EP2581409A1 - Vulcanisable compounds on the basis of nitrile rubbers containing epoxy groups - Google Patents

Abstract

Vulcanizable composition comprises (i) at least one epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber containing repeating units derived from e.g. at least one conjugated diene, (ii) at least one Lewis- and/or Bronsted base as a crosslinking agent, (iii) at least one crosslinking accelerator comprising thiuram, xanthates, thioureas, dithiocarbamates, and carbamates, (iv) less than 2.5 pts. wt. further crosslinking agents different from the component (ii), and (v) less than 2.5 pts. wt. further crosslinking accelerator different from the component (iii). Vulcanizable composition comprises (i) at least one epoxy group-containing and optionally completely or partially hydrogenated nitrile rubber containing repeating units derived from e.g. at least one conjugated diene, (ii) at least one Lewis- and/or Bronsted base as a crosslinking agent, (iii) at least one crosslinking accelerator comprising thiuram, xanthates, thioureas, dithiocarbamates, and carbamates, where the component (ii) is different from the component (iii), (iv) less than 2.5 pts. wt. (based on 100 pts. wt. component (i)) further crosslinking agents different from the component (ii), and (v) less than 2.5 pts. wt. (based on 100 pts. wt. component (i)) further crosslinking accelerator different from the component (iii). Independent claims are also included for: (1) preparing the above vulcanizable composition, comprising mixing the component (i) with the component (ii); (2) producing vulcanizates based on the component (i), comprising crosslinking the vulcanizable composition by increasing the temperature to 20-250[deg] C, preferably 50-230[deg] C; and (3) vulcanizates comprising the component (i).

Description

The invention relates to vulcanizable compositions based on epoxy group-containing, optionally completely or partially hydrogenated nitrile rubbers and special crosslinkers, a process for their preparation, a process for the preparation of vulcanizates thereof, the vulcanizates thus obtained and fully or partially hydrogenated nitrile rubbers containing epoxy groups.

Nitrile rubbers, also abbreviated to "NBR" for short, are understood to mean rubbers which are copolymers or terpolymers of at least one α, β-unsaturated nitrile, at least one conjugated diene and optionally one or more further copolymerizable monomers. Hydrogenated nitrile rubbers ("HNBR") are understood to mean corresponding copolymers or terpolymers in which the C =C double bonds of the copolymerized diene units are completely or partially hydrogenated.

Both NBR and HNBR have been firmly established in the field of specialty elastomers for many years. They have an excellent property profile in terms of excellent oil resistance, good heat resistance, excellent resistance to ozone and chemicals, the latter being even more pronounced in the case of HNBR than NBR. NBR and HNBR also have very good mechanical and performance properties. For this reason, they are widely used in a variety of applications and are used, for example, for the production of seals, hoses, belts and damping elements in the automotive sector, also for stators, borehole seals and valve seals in the field of oil production and also for many parts of the electrical industry, the machine industry. and shipbuilding. Commercially available are a variety of different types, which are characterized by different monomers, molecular weights, polydispersities and mechanical and physical properties depending on the application. In addition to the standard types, special types are increasingly in demand, which are increasingly in demand due to the content of special termonomers or special functionalizations.

In the practical use of (H) NBR rubbers, the vulcanization of the rubbers, ie in particular the crosslinker system and the vulcanization conditions, is of increasing importance. In addition to the classic rubber crosslinking systems based on peroxides or sulfur, which have existed for many decades, various new concepts for alternative crosslinking have been developed in recent years. Such crosslinking concepts also include polymers that are not accessible to all crosslinking forms and agents due to functional groups and therefore present a particular challenge.

In US-A-4,094,831 is the crosslinking of co- or terpolymers of conjugated C ₄ -C ₁₀ -conjugated dienes, optionally additionally C ₂ -C ₁₄ -olefins and an epoxy group-containing monomer by using mono- and polyamines, mono- and polyanhydrides and mono- and polycarboxylic acids. Acrylonitrile is not used as a monomer for the preparation of these copolymers or terpolymers.

In Polymer 46 (2005) 7632-7643 describes the preparation of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymers (ABS-g-GMA) by emulsion polymerization. From this ABS-g-GMA polymer, a blend is then produced with polybutylene terephthalate (PBT). It reports a good dispersibility of the ABS-g-GMA particles in the PBT matrix, which is attributed to a reaction between the carboxyl / hydroxy groups of the PBT chain ends and the epoxy groups of the GMA units at the interface.

In WO-A-02/46254 are functionalized Quaterpolymere based on conjugated dienes, vinyl-substituted aromatic compounds, olefinically unsaturated nitriles and hydroxyl-containing or epoxy-containing monomers, rubber mixtures based thereon and their use for the production of rubber moldings of all kinds described. The rubber mixtures may according to page 8, line 27 and page 9, lines 18-19 contain the usual crosslinkers. On page 9, lines 28 to 30 as crosslinkers, for example, elemental sulfur and sulfur donors, such as polysulfides, such as dithiocarbamates and Thiurampolysulfide called. It is generally stated that in addition to the crosslinker vulcanization accelerators can be used (eg amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates, xanthates and sulfonamides (page 9, lines 25, 26).) It is stated that these additives are used in conventional amounts (page 9, line 21) Whether and in what form the compression set of corresponding moldings can be influenced at high temperatures and in the long-term load by specially composed crosslinking systems is WO-A-2002/46254 not to be taken. According to the examples of WO-A-02/46254 The sulfur crosslinker is used in amounts of 1.5 parts by weight based on 100 parts by weight of all rubbers contained in the vulcanizable mixture.

JP-A-2005/120143 relates to rubbers containing repeating units of an unsaturated nitrile, at least one acrylic ester, an epoxy monomer, at least one non-conjugated cyclic polyene and optionally further unsaturated monomers, such as butadiene. For the crosslinking, sulfur, organic peroxides or metal salts of aromatic or aliphatic carboxylic acids or their anhydrides are mentioned.

In European Polymer Journal 37 (2001), pages 547-557 Glycidyl methacrylate-grafted nitrile rubbers are described which are used as compatibilizers in polymer blends. They are prepared by peroxidically initiated grafting reaction of glycidyl methacrylate on the NBR rubber.

In EP-A-0 160 399 Quaterpolymere be described based on a cyano-substituted alkyl (meth) acrylate, an alkyl acrylate, a crosslinkable monomer and another unsaturated monomer for applications especially in the automotive sector, where a high operating temperature, a good resistance to ozone and acid gasoline or gasohol be required. As the crosslinkable monomer, an epoxy group-containing monomer can also be used. For crosslinking unsaturated sulfur polymers, sulfur donors or peroxides are called in existing epoxy groups, the crosslinking of these by polyamines and their salts, ammonium compounds or in combination with conventional crosslinking systems.

In Polymer 40 (1999), pages 3665-3676 is described to use a special methyl methacrylate / glycidyl methacrylate / ethyl acrylate terpolymer (MGE) to increase the compatibility of polybutylene terephthalate (PBT) with acrylonitrile-butadiene-styrene terpolymers (ABS) in blends. It is stated that residual amounts of acids in the ABS produced by emulsion polymerization can lead to crosslinking reactions involving the epoxy functionalities of MGE. It is described that oxazolines can be formed from nitrile and epoxide functions as a follow-up reaction or carboxy groups are formed from nitriles by hydrolysis, which can likewise react with epoxy groups. Evidence is presented that these crosslinks have a detrimental effect on the mechanical properties of the ABS and the blend, and further conclude that strong acids can cause the formation of a gel or network in the SAN matrix, provided the MGE terpolymer is present.

In US 5,334,666 A vulcanizable epoxy group-containing elastomer compositions are described. These compositions comprise an epoxy group-containing elastomer and a crosslinker system comprising (1) an organic compound having two structural elements -C (= X) -NH-C (= Y) - wherein X and X independently represent oxygen or sulfur, and (2) a quaternary compound selected from quaternary ammonium salts and quaternary phosphonium salts . The organic compound (1) is preferably a heterocyclic, aromatic or aliphatic compound. The heterocyclic compounds preferably include parbanic acid, aloxan, aloxantine, aloxan-5-oxime, barbituric acid, 5-hydroxybarbituric acid, 5-benzalbarbituric acid, 5-aminobarbituric acid, 5-hydroxyiminobarbituric acid, 5,5-diethylbarbituric acid, 5-ethyl-5-phenylbarbituric acid, 5- (1-methylbutyl) -5- (allyl) barbituric acid, 5,5-diallylbarbituric acid, isocyanuric acid and pseudo-uric acid, and compounds in which the oxygen in the above heterocyclic compounds is replaced by a sulfur atom For example, 2,4-dithiobarbituric acid and 2-thiobarbituric acid. Preferred aromatic compounds are pyromelite diimide, melittriimide and 1,4,5,8-naphthaldiimide and the corresponding thioimides. Examples of aliphatic compounds are triuret, 1-methyltriuret, 1,1-diethyltriuret and tetrauret and the corresponding thioureas. In Example 5, an epoxy group-containing butadiene / acrylonitrile copolymer elastomer is vulcanized with the aid of a crosslinker. As crosslinkers according to Table 10 of US-A-5,334,666 Mixtures of isocyanuric acid (1.8 phr) and OTMeABr (octadecyltrimethylammonium bromide) (1.6 phr), 5,5-diethylbarbituric acid (2.5 phr) and OTMeABr (1.6 phr) and of isocyanuric acid (1.8 phr) and CePyBr (cetylpyridinium bromide) (1.4 phr). According to the comparative example, only 1 phr of ammonium benzoate is used as crosslinker.

JP 01-113477 A relates to an adhesive obtained by adding a crosslinker (eg Nadic methyl anhydride, ie methyl 5-norbornene-2,3-dicarboxylic anhydride) to a base component comprising 100 parts by weight of an epoxy resin, 1 to 40% by weight. Parts of a rubber obtained by grafting epoxy group-containing polymerizable monomers (eg, glycidyl methacrylate) onto the rubber (eg, acrylonitrile-butadiene copolymer); and 1 to 20 parts by weight of fine solid rubber particles obtainable by dispersing a usually liquid or dissolved solid Epoxy resin in a liquid rubber, and then vulcanization of the rubber. Described is the use of conventional crosslinkers such as sulfur, sulfur compounds and the ability to use thiuram, xanthates, thioureas, dithiocarbonates as accelerators.

Out US 2010/0152365 A1 is a carboxylic acid-modified nitrile copolymer latex is known which is used for the production of moldings and which can not trigger allergic reactions due to the absence of sulfur and a vulcanization accelerator and has other positive properties. As the crosslinkable unsaturated monomer, the copolymer latex may contain glycidyl (meth) acrylate. As a crosslinker, an ionic crosslinker can be used, which does not trigger allergic reactions. In claim 16 in US 2010/0152365 A1 Zinc oxide is called an ionic crosslinker. US 2010/0152365 A1 However, it does not describe whether and in which way, by selecting a suitable crosslinker system, the compression set can be improved at higher temperatures and long exposure times.

Out US-A-4,650,834 epoxy group-containing elastomer compositions are known which, in addition to an epoxy group-containing elastomer (1) a polycarboxylic acid having at least two (2) a quaternary compound selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts, and (3) a processing aid. The mixture of components (1) and (2) is used as a crosslinker. In Example 5, a terpolymer based on butadiene, acrylonitrile and glycidyl methacrylate is vulcanized by means of a crosslinker system. The crosslinker used is cetyltrimethylammonium bromide (2phr) / tetradecanedioic acid (2.2 phr) or tetrabutylphosphonium bromide (1.5phr) / tetradecanedioic acid (2.2 phr).

The object of the present invention was to provide a thermally stable crosslinking system for epoxide group-containing nitrile rubbers, which can be substantially reduced or completely avoided in vulcanizable compositions based on such epoxy-containing nitrile rubbers, the use of peroxide or sulfur crosslinkers and the compression set at high temperatures and in particular long exposure times are further improved.

The novel crosslinking system is said to avoid the disadvantages of existing crosslinkers, to be easily incorporated into the vulcanizable nitrile rubber compositions, and to allow a crosslinking reaction under uncomplicated conditions without causing side reactions such as e.g. Acid-base reactions with other additives of the vulcanizable composition such as e.g. Age protection occur. The crosslinkers used should have a good handleability and be used successfully for epoxide-containing nitrile rubbers as well as epoxide group-containing hydrogenated nitrile rubbers. The crosslinked epoxide group-containing (H) NBR rubbers should have very good to very good values in the compression set test, especially at high temperatures and in long-term use, show a good combination of elongation at break and tensile stress and thus an alternative or improvement to the conventional systems Offer.

1. (i) mindestens einen Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuk, der Wiederholungseinheiten abgeleitet von mindestens einem konjugierten Dien, mindestens einem α,β-ungesättigten Nitril und gegebenenfalls einem oder mehreren weiteren copolymerisierbaren Monomeren, jedoch keinem nicht-konjugierten cyclischen Polyen enthält
2. (ii) mindestens eine Lewis- und/oder Brönstedt-Base als Vernetzer, und
3. (iii) mindestens einen Vernetzungsbeschleuniger ausgewählt aus der Gruppe bestehend aus Thiuramen, Xanthogenaten, Thioharnstoffen, Dithiocarbamaten und Carbamaten,

wobei die Lewis- und/oder Brönstedt-Base (ii) verschieden sein muss von der definierten Gruppe der Vernetzungsbeschleuniger (iii), ferner in der vulkanisierbaren Zusammensetzung andere Vernetzer als die unter (ii) genannten nur in einer Menge unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind und andere Vernetzungsbeschleuniger als die unter (iii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind. The object is achieved by containing a vulcanizable composition

1. (I) at least one epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber containing repeating units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile and optionally one or more other copolymerizable monomers, but no non-conjugated cyclic polyene
2. (ii) at least one Lewis and / or Bronsted base as crosslinker, and
3. (iii) at least one crosslinking accelerator selected from the group consisting of thiurams, xanthogenates, thioureas, dithiocarbamates and carbamates,

wherein the Lewis and / or Bronsted base (ii) must be different from the defined group of crosslinking accelerators (iii), and in the vulcanizable composition other crosslinkers than those mentioned under (ii) only in an amount below 2.5 wt. Parts based on 100 parts by weight of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) are included and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i) are included.

The proviso that the Lewis and / or Bronsted base (ii) must be different from the defined group of crosslinking accelerators (iii), applies to all other embodiments, even if not explicitly mentioned.

Surprisingly, thermally stable networks can be built up in the vulcanizable composition when using the abovementioned crosslinkers (ii) according to the invention in combination with at least one crosslinking accelerator (iii). The crosslinking or vulcanization is catalyzed by the Lewis or Bronsted base (s) and the crosslinking accelerator (iii).

The amount of other crosslinkers used, e.g. Sulfur, sulfur donors and peroxides and other crosslinking accelerators can be drastically reduced, or it can even be completely dispensed with.

• andere Vernetzungsbeschleuniger als die unter (iii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des Epoxygruppen-halitgen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) und gleichzeitig
• andere Vernetzer als die unter (ii) genannten maximal bis zu einer Menge von 2,3 Gew.-Teilen, bevorzugt maximal bis zu einer Menge von 2,25 Gew.-Teilen, besonders bevorzugt maximal bis zu einer Menge von 2 Gew.-Teilen, ganz besonders bevorzugt maximal bis zu einer Menge von 1,5 Gew.-Teilen, inbesondere maximal bis zu einer Menge von 1 Gew.-Teil, inbesondere bevorzugt maximal bis zu einer Menge von 0,5 Gew.-Teilen und insbesondere besonders bevorzugt maximal bis zu einer Menge von 0,4 Gew.-Teilen, jeweils auch bezogen auf 100 Gew.-Teile des Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i).

In one embodiment, the vulcanizable composition contains

• crosslinking accelerators other than those mentioned under (iii) only in an amount of less than 2.5 parts by weight based on 100 parts by weight of the epoxy group halide, optionally completely or partially hydrogenated nitrile rubber (i) and simultaneously
• crosslinking agents other than those specified under (ii), up to a maximum of 2.3 parts by weight, preferably not more than 2.25 parts by weight, more preferably not more than 2 parts by weight. Parts, most preferably maximum up to an amount of 1.5 parts by weight, in particular at most up to an amount of 1 part by weight, more preferably at most up to an amount of 0.5 parts by weight and especially particularly preferably up to a maximum of 0.4 parts by weight, in each case based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i).

• andere Vernetzer als die unter (ii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) und gleichzeitig
• andere Vernetzungsbeschleuniger als die unter (iii) genannten maximal bis zu einer Menge von 2,3 Gew.-Teilen" bevorzugt maximal bis zu einer Menge von 2,25 Gew.-Teilen, besonders bevorzugt maximal bis zu einer Menge von 2 Gew.-Teilen, ganz besonders bevorzugt maximal bis zu einer Menge von 1,5 Gew.Teilen, inbesondere maximal bis zu einer Menge von 1 Gew.-Teil, inbesondere bevorzugt maximal bis zu einer Menge von 0,5 Gew.-Teilen und insbesondere besonders bevorzugt maximal bis zu einer Menge von 0,4 Gew.-Teilen, jeweils auch bezogen auf 100 Gew.-Teile des Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i).

In a further embodiment, the vulcanizable composition contains

• crosslinking agents other than those mentioned under (ii) only in an amount of less than 2.5 parts by weight based on 100 parts by weight of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) and simultaneously
• crosslinking accelerators other than those specified under (iii), up to a maximum of 2.3 parts by weight, preferably up to a maximum of 2.25 parts by weight, more preferably not more than 2 parts by weight. Parts, most preferably maximum up to an amount of 1.5 parts by weight, in particular maximum up to an amount of 1 part by weight, more preferably at most up to an amount of 0.5 parts by weight and particularly particularly preferably maximum up to an amount of 0.4 parts by weight, in each case based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i).

• andere Vernetzer als die unter (ii) genannten nur in einer Menge von bis zu 1 Gew.-Teil bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) und gleichzeitig
• andere Vernetzungsbeschleuniger als die unter (iii) genannten maximal bis zu einer Menge von 2,3 Gew.-Teilen, bevorzugt maximal bis zu einer Menge von 2,25 Gew.-Teilen, besonders bevorzugt maximal bis zu einer Menge von 2 Gew.-Teilen, ganz besonders bevorzugt maximal bis zu einer Menge von 1,5 Gew.-Teilen, inbesondere maximal bis zu einer Menge von 1 Gew.-Teil, inbesondere bevorzugt maximal bis zu einer Menge von 0,5 Gew.-Teilen und insbesondere besonders bevorzugt maximal bis zu einer Menge von 0,4 Gew.-Teilen, jeweils auch bezogen auf 100 Gew.-Teile des Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i).

In a further embodiment, the vulcanizable composition contains

• crosslinking agents other than those mentioned under (ii) only in an amount of up to 1 part by weight based on 100 parts by weight of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) and simultaneously
• other crosslinking accelerators than those specified under (iii), up to a maximum of 2.3 parts by weight, preferably not more than 2.25 parts by weight, more preferably not more than 2 parts by weight. Parts, most preferably maximum up to an amount of 1.5 parts by weight, in particular at most up to an amount of 1 part by weight, more preferably at most up to an amount of 0.5 parts by weight and especially particularly preferably up to a maximum of 0.4 parts by weight, in each case based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i).

• andere Vernetzer als die unter (ii) genannten maximal bis zu einer Menge von 2,3 Gew.-Teilen und gleichzeitig andere Vernetzungsbeschleuniger als die unter (iii) genannten maximal bis zu einer Menge von 2,3 Gew.-Teilen,
• bevorzugt andere Vernetzer als die unter (ii) genannten maximal bis zu einer Menge von 2,25 Gew.-Teilen und gleichzeitig andere Vernetzungsbeschleuniger als die unter (iii) genannten maximal bis zu einer Menge von 2,25 Gew.-Teilen,
• besonders bevorzugt andere Vernetzer als die unter (ii) genannten maximal bis zu einer Menge von 2 Gew.-Teilen und gleichzeitig andere Vernetzungsbeschleuniger als die unter (iii) genannten maximal bis zu einer Menge von 2 Gew.-Teilen,
• ganz besonders bevorzugt andere Vernetzer als die unter (ii) genannten maximal bis zu einer Menge von 1,5 Gew.-Teilen und gleichzeitig andere Vernetzungsbeschleuniger als die unter (iii) genannten maximal bis zu einer Menge von 1,5 Gew.-Teilen,
• insbesondere andere Vernetzer als die unter (ii) genannten maximal bis zu einer Menge von 1 Gew.-Teil und gleichzeitig andere Vernetzungsbeschleuniger als die unter (iii) genannten maximal bis zu einer Menge von 1 Gew.-Teil,
• insbesondere bevorzugt andere Vernetzer als die unter (ii) genannten maximal bis zu einer Menge von 0,5 Gew.-Teilen und andere Vernetzungsbeschleuniger als die unter (iii) genannten maximal bis zu einer Menge von 0,5 Gew.-Teilen,
• insbesondere besonders bevorzugt andere Vernetzer als die unter (ii) genannten maximal bis zu einer Menge von 0,4 Gew.-Teilen und andere Vernetzungsbeschleuniger als die unter (iii) genannten maximal bis zu einer Menge von 0,4 Gew.-Teilen und
• insbesondere ganz besonders bevorzugt überhaupt keinen anderen Vernetzer als die unter (ii) genannten und überhaupt keinen anderen Vernetzungsbeschleuniger als die unter (iii) genannten aufweist.

In a further embodiment, the vulcanizable composition comprises, in each case based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i),

• crosslinking agents other than those specified under (ii), up to a maximum of 2.3 parts by weight and simultaneously other crosslinking accelerators than those mentioned under (iii), up to a maximum of 2.3 parts by weight,
• preferably crosslinkers other than those mentioned under (ii) up to a maximum of 2.25 parts by weight and at the same time other crosslinking accelerators than those mentioned under (iii) up to a maximum of 2.25 parts by weight,
• particularly preferred crosslinking agents other than those mentioned under (ii) up to a maximum of 2 parts by weight and at the same time other crosslinking accelerators than those mentioned under (iii) up to a maximum of 2 parts by weight,
• very particular preference is given to cross-linking agents other than those mentioned under (ii) in a maximum amount of up to 1.5 parts by weight and at the same time other crosslinking accelerators than those mentioned under (iii), up to a maximum of 1.5 parts by weight,
• in particular crosslinking agents other than those mentioned under (ii), up to a maximum of 1 part by weight and at the same time other crosslinking accelerators than those mentioned under (iii), up to a maximum of 1 part by weight,
• particular preference is given to cross-linking agents other than those specified under (ii) up to a maximum of 0.5 parts by weight and cross-linking accelerators other than those mentioned under (iii), up to a maximum of 0.5 parts by weight,
• in particular, particularly preferred crosslinking agents other than those mentioned under (ii) up to a maximum of 0.4 parts by weight and other crosslinking accelerators than those mentioned under (iii) up to a maximum of 0.4 parts by weight and
• in particular, very particularly preferably does not have any crosslinker other than that mentioned under (ii) and has no crosslinking accelerator at all other than that mentioned under (iii).

In a further embodiment of the vulcanizable composition, the sum of other crosslinking agents than the one mentioned under (ii) and other crosslinking accelerators than that mentioned under (iii) is at a maximum of 2.5 parts by weight, preferably at most in an amount of 2.25 parts by weight, particularly preferably not more than 2 parts by weight, most preferably not more than 1.5 parts by weight, in particular not more than 1 part by weight, in particular preferably at most at an amount of 0.5 parts by weight and particularly particularly preferably at a maximum of 0.4 parts by weight, based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i ).

All of the abovementioned embodiments, which are preferred in any form, with regard to the correspondingly stated reduced maximum contents for the presence of crosslinkers other than those mentioned under (ii) and the presence of crosslinking accelerators other than those mentioned under (iii), also apply to the preferred embodiments specified in the context of this application vulcanizable composition having a more specific chemical definition of components (i), (ii) and / or (iii).

If the vulcanizable composition contains one or more rubbers other than those mentioned under (i), all of the abovementioned maximum amounts and their preferred embodiments relate to crosslinkers other than those mentioned under (ii) and crosslinking accelerators other than those mentioned under (ii). iii) to 100 parts by weight of Sum of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) and all other rubbers contained in the composition.

Compared to vulcanizable compositions which contain no crosslinking accelerator (iii) in addition to the crosslinker (ii), the vulcanizable compositions according to the invention have the advantage of leading to vulcanizates having an improved, ie lower compression set, in particular at relatively high temperatures, and often in shorter crosslinking times.

It is possible that the vulcanizable composition has no crosslinkers other than the crosslinker (ii) and no crosslinking accelerator at all other than that mentioned under (iii). In addition, it is possible to dispense with the use of known cocatalysts, so that heavy metal-free vulcanizates are accessible. In one embodiment, the vulcanizable composition contains no cocatalysts, especially no heavy metal-containing cocatalysts. In a further embodiment, the vulcanizable composition according to the invention contains no crosslinkers other than the crosslinker (s) (ii) and at the same time also no crosslinking accelerator other than that mentioned in (iii) and furthermore no cocatalysts, in particular no heavy metal-containing cocatalysts. The crosslinking density can be controlled by the proportion of the epoxy groups in the nitrile rubber and can be adjusted in wide ranges. The vulcanizates obtained show excellent values in the compression set at temperatures from room temperature to temperatures of 150 ° C.

In one embodiment, the nitrile rubber may also be a fully or partially hydrogenated nitrile rubber, in which the C =C double bonds present in the repeat units of the nitrile rubber are completely or partially hydrogenated.

Crosslinker (ii): Lewis and / or Bronsted base (s)

As Lewis or Brönsted bases, any suitable inorganic or organic bases may be used, but these may not be selected from the list of compounds which fall under the defined group of vulcanization accelerators (iii). It has been found that Lewis bases, which are electron pair donors, or Brönstedt bases, which represent proton acceptors and a pK _B value in the range of -12 to +13, preferably in the range of -11 to +12, particularly preferably in the range of -10.5 to +10, most preferably in the range of -10 to +9.5 and in particular in the range of -10 to +8 have to use.

The vulcanizable composition according to the invention as crosslinker (ii) preferably comprises at least one inorganic or organic Bronsted and / or Lewis base.

Lewis bases:

1. (a) Übergangs- oder Halbmetalle, Aluminium, Gallium, Indium, Zinn, Thallium oder Blei in ihrer elementaren Form eingesetzt werden oder
2. (b) Alkyl- oder Arylverbindungen, Ester, Salze, Komplexverbindungen oder Oxide der Alkali-, Erdalkali-, Übergangs- oder Halbmetalle, von Aluminium, Gallium, Indium, Zinn, Thallium, Blei, Stickstoff, Sauerstoff oder Phosphor,

As Lewis bases, as far as these are electron pair donors,

1. (a) transition or semi-metals, aluminum, gallium, indium, tin, thallium or lead are used in their elemental form or
2. (b) alkyl or aryl compounds, esters, salts, complex compounds or oxides of the alkali metals, alkaline earth metals, transition metals or semimetals, of aluminum, gallium, indium, tin, thallium, lead, nitrogen, oxygen or phosphorus,

1. (a) Übergangs- oder Halbmetalle, Aluminium, Indium oder Zinn in elementarer Form eingesetzt oder
2. (b) Alkyl- oder Arylverbindungen, Ester, Salze, Komplexverbindungen oder Oxide der Alkali-, Erdalkali-, Übergangs- oder Halbmetalle, von Alumnium, Indium, Zinn, Stickstoff, Sauerstoff oder Phosphor

Preference is given as Lewis bases, as far as these are each electron pair donors,

1. (A) transition or semi-metals, aluminum, indium or tin used in elemental form or
2. (b) alkyl or aryl compounds, esters, salts, complex compounds or oxides of the alkali, alkaline earth, transition or semimetals, of aluminum, indium, tin, nitrogen, oxygen or phosphorus

Particularly preferred Lewis bases are crown ethers, in particular 12-crown-4, cryptands, in particular [2.2.2] cryptand, ammonia, tetraalkylammonium salts, in particular tetraalkylammonium bromides, benzyltrialkylammonium salts, tetraalkylphosphonium salts, benzyltrialkylphosphonium salts, triphenylphosphine, sodium or potassium cyanide, sodium iodide, bipyridine , Phenantroline, tetrahydrofuran, cyclooctadiene, hydrazine or diethyl ether.

Brönsted bases:

As Bronsted base (s) are preferably those selected from the group consisting of sulfates, sulfites, sulfides, phosphates, carbonates, substituted or unsubstituted amines, substituted or unsubstituted, aromatic or non-aromatic nitrogen-containing organic heterocycles, substituted or unsubstituted urea derivatives, guanidines and their derivatives, hydroxides of alkali or alkaline earth metals, salts of inorganic or organic sulfonic, carboxylic and phophonic acids, their mono- or diesters and organometallic compounds of the alkali metals lithium, sodium and potassium used.

Preferred carbonates are sodium carbonate, potassium carbonate, calcium carbonate and lithium carbonate.

Preferred substituted or unsubstituted amines are ammonia, triethylamine, diisopropylamine and triethanolamine.

Preferred substituted or unsubstituted, aromatic or non-aromatic nitrogen-containing organic heterocycles are pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, tetramethylethylenediamine, pyrrolidine, pyrazole, Piperidine, pyrrole and imidazole.

Preferred substituted or unsubstituted urea derivatives are urea, biuret, dimethylurea and N, N'-dimethylpropyleneurea.

Preferred salts of sulfonic acids are sodium alkylbenzylsulfonic acids , especially sodium dodecylbenzylsulfonic acid.

Preferred salts of the phosphonic acids are sodium or potassium salts of 1-hydroxyethane- (1,1-diphosphonic acid), aminotrimethylenephosphonic acid and ethylenediaminetetra (methylenephosphonic acid).

Preferred salts of the carboxylic acids are sodium or potassium salts of ascorbic acid, acetic acid, propionic acid, acrylic acid, fumaric acid, maleic acid, benzoic acid, abietic acid and saturated and unsaturated fatty acids such as stearic acid and oleic acid.

Preferred organometallic compounds of the elements lithium, sodium and potassium are sodium ethoxide, sodium methaolate, butyl lithium, lithium diisopropylamide and potassium ethanolate.

Component (iii): crosslinking accelerator

In the vulcanizable compositions of this invention, at least one crosslinking accelerator selected from the group consisting of thiurams, xanthogenates, thioureas, dithiocarbamates and carbamates is used as component (iii).

In a preferred embodiment, the vulcanizable composition contains, as component (iii), at least one crosslinking accelerator selected from the group consisting of thiurams, xanthogenates, dithiocarbamates and carbamates.

They are often so fast in their vulcanization behavior that, because of their reactivity, they are practically not used in conventional crosslinking systems.

Preferred thiurams are thiuram monosulphide, thiuram disulphide or thiurampol sulphides. Examples of preferred thiurams are tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), dipentamethylenethiuram tetrasulfide (DPTT), dipentamethylene thiuram hexasulfide (DPTH), dipentamethylene diuram monosulfide (DPTM), dipentamethylene thiuram disulfide (DPTD), N, N'-diethyl-N, N ' diphenylthiuram disulfide (EPTDM) or dimethyldiphenyl thiuram disulfide (MPTD).

As xanthates preferably the alkali metal or zinc salts of xanthates and Arylguanidinxanthogenate eligible. Examples of preferred xanthates are arylguanidinium xanthates, bisxanthogenates or polyxanthogenates, zinc isopropylxanthogenate (ZIX) or its water-soluble sodium salt (NaIX).

Preferred thioureas are ethylenethanol (ETU), diphenylthiourea (DPTU), 1,3-di-o-tolylthiourea (DTTU) or diethyltiourea (DPTU).

Preferred dithiocarbamates are the metal and ammonium dithiocarbamates . Examples of preferred dithiocarbamates are zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc ethylphenyldithiocarbamate (ZEPC), zinc dibenzyl dithiocarbamate (ZDBC), zinc pentamethylenedithiocarbamate (ZPD), zinc-N-pentamethylendithiocarbamat (Z5MC) Zinklupetidindindithiocarbamat (ZLD), zinc dialkyldithiophosphate ( ZDT), zinc 2-ethylhexanoate (ZEH), Zinkdinonyldithiocarbamat (ZNDNC), bismuth dimethyl dithiocarbamate (BIDD), nickel (NDBC) Seleniumdiethyldithiocarbamate (SeedC), selenium dimethyldithiocarbamate (SeDMC), sodium diethyldithiocarbamate (SEDC) Telluriumdiethyldithiocarbamat (TeEDC) Telluriumdiethyldithiocarbamate (TeDEC), sodium dimethyldithiocarbamate (SMDC), sodium dibutyldithiocarbamate (SBC) or sodium cyclohexylethyldithiocarbamate (SHEC).

The preferred carbamate is hexamethylenediaminocarbamate.

1. (i) mindestens einen Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuk, der Wiederholungseinheiten abgeleitet von mindestens einem konjugierten Dien, mindestens einem α,β-ungesättigten Nitril und gegebenenfalls einem oder mehreren weiteren copolymerisierbaren Monomeren, jedoch keinem nicht-konjugierten cyclischen Polyen enthält,
2. (ii) mindestens eine Lewis- und/oder Brönstedt-Base als Vernetzer und
3. (iii) mindestens einen Vernetzungsbeschleuniger ausgewählt aus der Gruppe bestehend aus Thiuramen, Xanthogenaten, Dithiocarbamaten und Carbamaten,
   wobei die Lewis- und/oder Brönstedt-Base (ii) verschieden sein muss von der definierten Gruppe der Vernetzungsbeschleuniger (iii), ferner in der vulkanisierbaren Zusammensetzung andere Vernetzer als die unter (ii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind und andere Vernetzungsbeschleuniger als die unter (iii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind.

Preference is given to containing a vulcanizable composition

1. (I) at least one epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber containing repeating units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile and optionally one or more other copolymerizable monomers, but no non-conjugated cyclic polyene .
2. (ii) at least one Lewis and / or Bronsted base as crosslinker and
3. (iii) at least one crosslinking accelerator selected from the group consisting of thiurams, xanthogenates, dithiocarbamates and carbamates,
   wherein the Lewis and / or Bronsted base (ii) must be different from the defined group of crosslinking accelerators (iii), and in the vulcanizable composition other crosslinkers than those mentioned under (ii) only in an amount of less than 2.5 wt Parts based on 100 parts by weight of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) are included and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight to 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i) are included.

1. (i) mindestens einen Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuk, der Wiederholungseinheiten abgeleitet von mindestens einem konjugierten Dien, mindestens einem α,β-ungesättigten Nitril und gegebenenfalls einem oder mehreren weiteren copolymerisierbaren Monomeren, jedoch keinem nicht-konjugierten cyclischen Polyen enthält,
2. (ii) mindestens eine Lewis-Base ausgewählt aus der Gruppe bestehend aus Kronenethern, Kryptanden, Tetraalkylammoniumbromiden, insbesondere Tetra-n-butylammoniumbromid, Triphenylphosphin und Bipyridin und/oder eine Brönstedt-Base ausgewählt aus der Gruppe bestehend aus Natriumcarbonat, Kaliumcarbonat, Calciumcarbonat, Lithiumcarbonat, Triethylamin, Diisopropylamin, Triethanolamin Pyridin, 1,8-Diazabicyclo[5.4.0]undec-7-en, 1,4-Diazabicyclo[2.2.2]octan, Tetramethylethylendiamin, Pyrrolidin, Pyrazol, Piperidin, Pyrrol, Imidazol, Harnstoff, Biuret, Dimethylharnstoff, N,N'-Dimethylpropylenharnstoff und Natrium-Dodecylbenzylsulfonsäure als Vernetzer,
3. (iii) mindestens einen Vernetzungsbeschleuniger ausgewählt aus der Gruppe bestehend aus Hexamethylendiaminocarbamat, Tetramethylthiuramdisulfid (TMTD), Tetramethylthiurammonosulfid (TMTM), Tetraethylthiuramdisulfid (TETD), Dipentamethylenthiurammonosulfid (DPTM), Dipentamethylenthiuramdisulfid (DPTD), Dimethyldiphenylthiuramdisulfid (MPTD), Arylguanidiniumxanthogenate, Zinkisopropylxanthogenat (ZIX), Ethylenthioharstoff (ETU), Diphenylthioharnstoff (DPTU), 1,3-Di-o-tolylthioharnstoff (DTTU), Diethyltioharnstoff (DPTU), Zinkdimethyldithiocarbamat (ZDMC), Zinkdiethyldithiocarbamat (ZDEC), Zinkdibutyldithiocarbamat (ZDBC), Zinkethylphenyldithiocarbamat (ZEPC), Zinkdibenzyldithiocarbamat (ZDBC), Zinkpentamethylendithiocarbamat (ZPD), Natriumdiethyldithiocarbamat (SEDC), Natriumdimethyldithiocarbamate(SMDC), Natriumdibutyldithiocarbamat (SBC) und Natriumcyclohexylethyldithiocarbamat (SHEC) wobei in der vulkanisierbaren Zusammensetzung andere Vernetzer als die unter (ii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des epoxygruppen-haltigen optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind und andere Vernetzungsbeschleuniger als die unter (iii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind.

In a preferred embodiment, the vulcanizable composition of the invention contains

1. (I) at least one epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber containing repeating units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile and optionally one or more other copolymerizable monomers, but no non-conjugated cyclic polyene .
2. (ii) at least one Lewis base selected from the group consisting of crown ethers, cryptands, tetraalkylammonium bromides, in particular tetra-n-butylammonium bromide, triphenylphosphine and bipyridine and / or a Bronsted base selected from the group consisting of sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate , Triethylamine, diisopropylamine, triethanolamine pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, tetramethylethylenediamine, pyrrolidine, pyrazole, piperidine, pyrrole, imidazole, urea, Biuret, dimethylurea, N, N'-dimethylpropyleneurea and sodium dodecylbenzylsulfonic acid as crosslinker,
3. (iii) at least one crosslinking accelerator selected from the group consisting of Hexamethylendiaminocarbamat, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), Dipentamethylenthiurammonosulfid (DPTM), dipentamethylenethiuram (DPTD) Dimethyldiphenylthiuramdisulfid (MPTD) Arylguanidiniumxanthogenate isopropylxanthogenate, zinc isopropylxanthogenate (ZIX) , Ethylene thiourea (ETU), diphenylthiourea (DPTU), 1,3-di-o-tolylthiourea (DTTU), diethyltiourea (DPTU), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc ethylphenyldithiocarbamate (ZEPC), zinc dibenzyldithiocarbamate (ZDBC), zinc pentamethylene dithiocarbamate (ZPD), sodium diethyldithiocarbamate (SEDC), sodium dimethyldithiocarbamate (SMDC), sodium dibutyldithiocarbamate (SBC), and sodium cyclohexylethyl dithiocarbamate (SHEC) wherein in the vulcanizable composition crosslinking agents other than those mentioned under (ii) are contained only in an amount of less than 2.5 parts by weight based on 100 parts by weight of the epoxy group-containing optionally fully or partially hydrogenated nitrile rubber (i), and crosslinking accelerators other than those mentioned under (iii) are present only in an amount of less than 2.5 parts by weight, based on 100 parts by weight of the epoxide group-containing, optionally fully or partially hydrogenated nitrile rubber (i).

The amount of the crosslinking agent (ii) and the crosslinking accelerator (iii) may be selected depending on the concentration of the epoxy groups in the nitrile rubber.

1. (i) mindestens einen Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuk, der Wiederholungseinheiten abgeleitet von mindestens einem konjugierten Dien, mindestens einem α,β-ungesättigten Nitril und gegebenenfalls einem oder mehreren weiteren copolymerisierbaren Monomeren, jedoch keinem nicht-konjugierten cyclischen Polyen enthält, und
2. (ii) 0,01 bis 30 Gew.-Teile, bevorzugt 0,05 bis 25 Gew.-Teile, besonders bevorzugt 0,1 bis 15 Gew.-Teile und insbesondere 0,2 bis 10 Gew.-Teile, jeweils auf 100 Gew.Teile des Nitrilkautschuks (i) bezogen, mindestens einer Lewis- und/oder Brönsted-Base als Vernetzer,
3. (iii) 0,01 bis 10 Gew.-Teile, bevorzugt 0,05 bis 7,5 Gew.-Teile, besonders bevorzugt 0,075 bis 5 Gew.-Teile und insbesondere 0,1 bis 3 Gew.-Teile, jeweils auf 100 Gew.Teile des Nitrilkautschuks (i) bezogen, mindestens eines Vernetzungsbeschleunigers ausgewählt aus der Gruppe bestehend aus Thiuramen, Xanthogenaten, Thioharnstoffen, Dithiocarbamaten und Carbamaten, bevorzugt ausgewählt aus der Gruppe bestehend aus Thiuramen, Xanthogenaten, Dithiocarbamaten und Carbamaten,
   wobei die Lewis- und/oder Brönstedt-Base (ii) verschieden sein muss von der definierten Gruppe der Vernetzungsbeschleuniger (iii), ferner in der vulkanisierbaren Zusammensetzung andere Vernetzer als die unter (ii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des epoxygruppen-haltigen optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind und andere Vernetzungsbeschleuniger als die unter (iii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind..

The vulcanizable composition usually contains

1. (I) at least one epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber containing repeating units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile and optionally one or more other copolymerizable monomers, but no non-conjugated cyclic polyene , and
2. (Ii) 0.01 to 30 parts by weight, preferably 0.05 to 25 parts by weight, particularly preferably 0.1 to 15 parts by weight and in particular 0.2 to 10 parts by weight, each to 100 Parts by weight of the nitrile rubber (i), at least one Lewis and / or Bronsted base as crosslinking agent,
3. (Iii) 0.01 to 10 parts by weight, preferably 0.05 to 7.5 parts by weight, more preferably 0.075 to 5 parts by weight and especially 0.1 to 3 parts by weight, each to 100 Parts by weight of the nitrile rubber (i), at least one crosslinking accelerator selected from the group consisting of thiurams, xanthogenates, thioureas, dithiocarbamates and carbamates, preferably selected from the group consisting of thiurams, xanthogenates, dithiocarbamates and carbamates,
   wherein the Lewis and / or Bronsted base (ii) must be different from the defined group of crosslinking accelerators (iii), and in the vulcanizable composition other crosslinkers than those mentioned under (ii) only in an amount of less than 2.5 wt Parts relative to 100 parts by weight of the epoxy group-containing optionally fully or partially hydrogenated nitrile rubber (i) are included and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i) are included ..

According to the invention, the Lewis and / or Bronsted bases and the crosslinking accelerator (iii) are added to the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber after its preparation. It is not a matter of compounds that are involved in the Production of the optionally completely or partially hydrogenated nitrile rubber or in its compounding are free or already present, but by separately dosed bases or the defined crosslinking accelerator. The additive is added to the nitrile rubber after its preparation. As a result, a partial crosslinking or partial gelation is already avoided during the production of the nitrile rubber.

Epoxy group-containing nitrile rubber:

As epoxy group-containing, optionally fully or partially hydrogenated nitrile rubbers (i) any suitable, optionally wholly or partially hydrogenated nitrile rubbers can be used in the vulcanizable compositions, the repeat units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile and optionally contain one or more other copolymerizable monomers, but no non-conjugated cyclic polyene and are epoxy group-containing.

The epoxy groups can either be applied to the nitrile rubber by subsequent grafting or grafting of epoxy group-containing compounds or else be due to repeat units of an epoxy group-containing monomer additionally used in the preparation of the nitrile rubber.

In the vulcanizable composition according to the invention, preference is given to using epoxy-group-containing, optionally fully or partially hydrogenated nitrile rubbers, the repeat units of at least one nitrile, at least one conjugated diene, at least one epoxy-group-containing monomer and optionally one or more further copolymerizable monomers, but none. conjugated cyclic polyenes, included.

The epoxy group-containing nitrile rubbers are usually prepared by co-polymerizing the aforementioned monomers to produce the epoxy group-containing nitrile rubber. In this case, there is no graft rubber grafted with epoxy group-containing monomers, but a rubber in which the epoxy group-containing monomer was incorporated into the polymer main chain in the course of the polymerization in the form of repeating units.

worin,

m

0 oder 1 ist,

X

für O, O(CR₂)_p, (CR₂)_pO, C(=O)O, C(=O)O(CR₂)_p, C(=O)NR, (CR₂)_p, N(R), N(R)(CR₂)_p, P(R), P(R)(CR₂)_p, P(=O)(R), P(=O)(R)(CR₂)_p, S, S(CR₂)_p, S(=O), S(=O)(CR₂)_p, S(=O)₂(CR₂)_p oder S(=O)₂ steht, wobei R in diesen Resten gleich oder verschieden ist und die gleiche Bedeutungen besitzen kann wie R¹-R⁶,

Y

für Wiederholungseinheiten eines oder mehrerer, ein- oder mehrfach ungesättigter Monomeren steht, umfassend konjugierte oder nicht-konjugierte Diene, Alkine und Vinylverbindungen, oder für ein Strukturelement, welches sich ableitet von Polymeren umfassend Polyether, insbesondere Polyalkylenglykolether und Polyalkylenoxide, Polysiloxane, Polyole, Polycarbonate, Polyurethane, Polyisocyanate, Polysaccharide, Polyester und Polyamide,

n und p

gleich oder verschieden sind und jeweils im Bereich von 0 bis 10.000 liegen,

R, R¹, R², R³, R⁴, R⁵ und R⁶

gleich oder verschieden sind und für H, einen linearen oder verzweigten, gesättigten, ein- oder mehrfach ungesättigten Alkylrest, einen gesättigten, ein- oder mehrfach ungesättigten Carbo- oder Heterocyclylrest, Aryl, Heteroaryl, Arylalkyl, Heteroarylalkyl, Alkoxy, Aryloxy, Heteroaryloxy, Amino, Amido, Carbamoyl, Alkylthio, Arylthio, Sulfanyl, Thiocarboxy, Sulfinyl, Sulfono, Sulfino, Sulfeno, Sulfonsäuren, Sulfamoyl, Hydroxyimino, Alkoxycarbonyl, F, Cl, Br, I, Hydroxy, Phosphonato, Phosphinato, Silyl, Silyloxy, Nitril, Borate, Selenate, Carbonyl, Carboxy, Oxycarbonyl, Oxysulfonyl, Oxo, Thioxo, Epoxy, Cyanate, Thiocyanate, Isocyanate, Thioisocyanate oder Isocyanide stehen.

Optional sind die für die Reste R, R¹ bis R⁶ und die Wiederholungseinheiten Y der allgemeinen Formel (I) genannten Bedeutungen jeweils ein- oder mehrfach substituiert.The epoxy group-containing monomers used to prepare the epoxy group-containing nitrile rubbers preferably have the general formula (I)

wherein,

m

0 or 1,

X

for O, O (CR ₂ ) _p , (CR ₂ ) _p O, C (= O) O, C (= O) O (CR ₂ ) _p , C (= O) NR, (CR ₂ ) _p , N (R), N (R) (CR ₂ ) _p , P (R), P (R) (CR ₂ ) _p , P (= O) (R), P (= O) (R) (CR ₂ ) _p , S, S (CR ₂ ) _p , S (= O), S (= O) (CR ₂ ) _p , S (= O) ₂ (CR ₂ ) _p or S (= O) ₂ , where R in these radicals the same or different and can have the same meanings as R ¹ -R ⁶ ,

Y

represents repeat units of one or more mono- or polyunsaturated monomers, comprising conjugated or nonconjugated dienes, alkynes and vinyl compounds, or a structural element derived from polymers comprising polyethers, in particular polyalkylene glycol ethers and polyalkylene oxides, polysiloxanes, polyols, polycarbonates, Polyurethanes, polyisocyanates, polysaccharides, polyesters and polyamides,

n and p

are the same or different and are each in the range of 0 to 10,000,

R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶

are the same or different and are H, a linear or branched, saturated, mono- or polyunsaturated alkyl radical, a saturated, mono- or polyunsaturated carbo- or heterocyclyl radical, aryl, heteroaryl, arylalkyl, heteroarylalkyl, alkoxy, aryloxy, heteroaryloxy, amino , Amido, carbamoyl, alkylthio, arylthio, sulfanyl, thiocarboxy, sulfinyl, sulfono, sulfino, sulfeno, sulfonic acids, sulfamoyl, hydroxyimino, alkoxycarbonyl, F, Cl, Br, I, hydroxy, phosphonato, phosphinato, silyl, silyloxy, nitrile, borates , Selenates, carbonyl, carboxy, oxycarbonyl, oxysulfonyl, oxo, thioxo, epoxy, cyanates, thiocyanates, isocyanates, thioisocyanates or isocyanides.

Optionally, the meanings given for the radicals R, R ¹ to R ⁶ and the repeating units Y of the general formula (I) are each mono- or polysubstituted.

Preferably, the following radicals from the meanings for R, R ¹ to R ⁶ have such a single or multiple substitution: alkyl, carbocyclyl, heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, alkoxy, aryloxy, alkylthio, arylthio, amino, amido , Carbamoyl, F, Cl, Br, I, hydroxy, phosphonato, phosphinato, sulfanyl, thiocarboxy, sulfinyl, sulfono, sulfino, sulfeno, sulfamoyl, silyl, silyloxy, carbonyl, carboxy, oxycarbonyl, oxysulfonyl, oxo, thioxo, borates, selenates and epoxy. Substituents are - as far as chemically stable compounds arise - all meanings in question, which can assume R. Particularly suitable as substituents are alkyl, carbocyclyl, aryl, halogen, preferably fluorine, chlorine, bromine or iodine, nitrile (CN) and carboxy.

Particular preference is given to using an epoxy group-containing monomer of the general formula (I) in which X, R, R ¹ to R ⁶ and m have the meanings given for the general formula (I), and p and n are identical or different and denote Range from 0 to 100.

worin
X, R, R¹ bis R⁶, m und p die zuvor für die allgemeine Formel (I) genannten Bedeutungen besitzen.Particularly preferably, X, R, R ¹ to R ⁶ and m have the meanings given above for the general formula (I) and p is in the range of 0 to 100 and n is equal to zero. This epoxy group-containing monomer thus has the general structure (Ia)

wherein
X, R, R ¹ to R ⁶ , m and p have the meanings given above for the general formula (I).

Particular preference is given to using an epoxy group-containing monomer of the general formula (I) in which X, R and R ¹ to R ^{6 have} the meanings given above for the general formula (I), m is 1 , p is 1 and n is equal to zero.

Preferred examples of epoxy group-containing monomers are 2-ethylglycidyl acrylate, 2-ethylglycidyl methacrylate, 2- (n-propyl) glycidyl acrylate, 2- (n-propyl) glycidyl methacrylate, 2- (n-butyl) glycidyl acrylate, 2- (n-butyl) glycidyl methacrylate , Glycidylmethylacrylate, glycidylmethylmethacrylate, glycidylacrylate, (3 ', 4'-epoxyheptyl) -2-ethylacrylate, (3', 4'-epoxyheptyl) -2-ethylmethacrylate, (6 ', 7'-epoxyheptyl) acrylate, (6 ', 7'-epoxyheptyl) methacrylate, allyl glycidyl ether, allyl 3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl glycidyl ether, vinyl 3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinyl benzyl glycidyl ether , m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 3-vinylcyclohexeneoxide.

As the epoxy group-containing monomer, a glycidyl (alkyl) acrylate is preferably used. Particular preference is given to using glycidyl acrylate or glycidyl methacrylate.

1. (i) mindestens einen Epoxygruppen-haltigen, optional ganz oder teiweise hydrierten Nitrilkautschuk, der Wiederholungseinheiten abgeleitet von mindestens einem konjugierten Dien, mindestens einem α,β-ungesättigten Nitril, mindestens einem Epoxygruppen-haltigen Monomer ausgewählt aus der Gruppe bestehend aus 2-Ethylglycidylacrylat, 2-Ethylglycidylmethacrylat, 2-(n-Propyl) glycidylacrylat, 2-(n-Propyl)glycidylmethacrylat, 2-(n-Butyl)glycidylacrylat, 2-(n-Butyl) glycidylmethacrylat, Glycidylmethylacrylat, Glycidylmethyl-methacrylat, Glycidylacrylat, (3',4'-Epoxyheptyl)-2-ethylacrylat, (3',4'-Epoxyheptyl)-2-ethyl-methacrylat, (6',7'-Epoxy-heptyl)acrylat, (6',7'-Epoxyheptyl)methacrylat, Allylglycidylether, Allyl-3,4-epoxy-heptylether, 6,7-Epoxyheptylallylether, Vinylglycidylether, Vinyl-3,4-epoxyheptylether, 3,4-Epoxyheptylvinylether, 6,7-Epoxyheptylvinylether, o-Vinylbenzylglycidylether, m-Vinylbenzylglycidylether, p-Vinylbenzylglycidylether und 3-Vinylcyclohexenoxid, und gegebenenfalls einem oder mehreren weiteren copolymerisierbaren Monomeren, jedoch keinem nicht-konjugierten cyclischen Polyen, enthält,
2. (ii) mindestens eine Lewis-Base ausgewählt aus der Gruppe bestehend aus Kronenether, Kryptanden, Tetraalkylammoniumbromiden, insbesondere Tetra-n-butylammoniumbromid, Triphenylphosphin und Bipyridin und/oder mindestens einer Brönstedt-Base ausgewählt aus der Gruppe bestehend aus Natriumcarbonat, Kaliumcarbonat, Calciumcarbonat, Lithiumcarbonat, Triethylamin, Diisopropylamin, Triethanolamin Pyridin, 1,8-Diazabicyclo[5.4.0]undec-7-en, 1,4-Diazabicyclo[2.2.2]octan, Tetramethylethylendiamin, Pyrrolidin, Pyrazol, Piperidin, Pyrrol, Imidazol, Harnstoff, Biuret, Dimethylharnstoff, N,N'-Dimethylpropylenharnstoff und Natrium-Dodecylbenzylsulfonsäure als Vernetzer, (iii) mindestens einen Vernetzungsbeschleuniger ausgewählt aus der Gruppe bestehend aus Hexamethylendiaminocarbamat, Tetramethylthiuramdisulfid (TMTD), Tetramethylthiurammonosulfid (TMTM), Tetraethylthiuramdisulfid (TETD), Dipentamethylenthiurammonosulfid (DPTM), Dipentamethylenthiuramdisulfid (DPTD), Dimethyldiphenylthiuramdisulfid (MPTD), Arylguanidiniumxanthogenate, Zinkisopropylxanthogenat (ZIX), Ethylenthioharstoff (ETU), Diphenylthioharnstoff (DPTU), 1,3-di-o-tolylthioharnstoff (DTTU), Diethyltioharnstoff (DPTU), Zinkdimethyldithiocarbamat (ZDMC), Zinkdiethyldithiocarbamat (ZDEC), Zinkdibutyldithiocarbamat (ZDBC), Zinkethylphenyldithiocarbamat (ZEPC), Zinkdibenzyldithiocarbamat (ZDBC), Zinkpentamethylendithiocarbamat (ZPD), Natriumdiethyldithiocarbamat (SEDC), Natriumdimethyldithiocarbamate(SMDC), Natriumdibutyldithiocarbamat (SBC) und Natriumcyclohexylethyldithiocarbamat (SHEC)
   wobei in der vulkanisierbaren Zusammensetzung andere Vernetzer als die unter (ii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen, bevorzugt nur bis zu 1 Gew. Teil und besonders bevorzugt nur bis zu 0,75 Gew.Teilen, bezogen auf 100 Gew.-Teile des epoxgruppen-haltigen optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind und andere Vernetzungsbeschleuniger als die unter (iii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen, bevorzugt nur bis zu 1 Gew. Teil und besonders bevorzugt nur bis zu 0,75 Gew.Teilen, bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind.

In a preferred embodiment, the vulcanizable composition of the invention contains

1. (i) at least one epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber, the repeat units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile, at least one epoxy group-containing monomer selected from the group consisting of 2-ethylglycidyl acrylate, 2-ethylglycidyl methacrylate, 2- (n-propyl) glycidyl acrylate, 2- (n-propyl) glycidyl methacrylate, 2- (n-butyl) glycidyl acrylate, 2- (n-butyl) glycidyl methacrylate, glycidylmethyl acrylate, glycidylmethyl methacrylate, glycidyl acrylate, (3 ', 4'-epoxyheptyl) -2-ethylacrylate, (3', 4'-epoxyheptyl) -2-ethyl-methacrylate, (6 ', 7'-epoxy-heptyl) acrylate, (6', 7'-epoxyheptyl) methacrylate, allyl glycidyl ether, allyl 3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl glycidyl ether, vinyl 3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether and 3-vinylcyclohexene oxide, and optionally one or more other copolymerizable monomers but not non-conjugated cyclic polyene,
2. (ii) at least one Lewis base selected from the group consisting of crown ethers, cryptands, tetraalkylammonium bromides, in particular tetra-n-butylammonium bromide, triphenylphosphine and bipyridine and / or at least one Bronsted base selected from the group consisting of sodium carbonate, potassium carbonate, calcium carbonate, Lithium carbonate, triethylamine, diisopropylamine, triethanolamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, tetramethylethylenediamine, pyrrolidine, pyrazole, piperidine, pyrrole, imidazole, urea , Biuret, dimethylurea, N, N'-dimethylpropyleneurea and sodium dodecylbenzylsulfonic acid crosslinking agent; (iii) at least one crosslinking accelerator selected from the group consisting of hexamethylenediaminocarbamate, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), dipentamethylenethiuram monosulfide (DPTM ), Dipentamethylenethiuram disulfide (DPTD), dimethyldiphenylthiuram disulfide fid (MPTD), arylguanidinium xanthogenates, zinc isopropylxanthogenate (ZIX), ethylene thiourea (ETU), diphenylthiourea (DPTU), 1,3-di-o-tolylthiourea (DTTU), diethyltiourea (DPTU), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), Zinc dibutyldithiocarbamate (ZDBC), zinc ethylphenyldithiocarbamate (ZEPC), zinc dibenzyldithiocarbamate (ZDBC), zinc pentamethylene dithiocarbamate (ZPD), sodium diethyldithiocarbamate (SEDC), sodium dimethyldithiocarbamate (SMDC), sodium dibutyldithiocarbamate (SBC) and sodium cyclohexylethyl dithiocarbamate (SHEC)
   wherein in the vulcanizable composition other crosslinking agents than those mentioned under (ii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 parts by weight, based to 100 parts by weight of the epox group-containing optionally whole or partially hydrogenated nitrile rubbers (i) are present and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 wt .Teilen, based on 100 parts by weight of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) are included.

1. (i) mindestens einen Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuk, der Wiederholungseinheiten abgeleitet von mindestens einem konjugierten Dien, mindestens einem α,β-ungesättigten Nitril, von Glycidylacrylat und/oder Glycidylmethacrylat und gegebenenfalls einem oder mehreren weiteren copolymerisierbaren Monomeren, jedoch keinem nicht-konjugierten cyclischen Polyen enthält,
2. (ii) mindestens eine Lewis-Base ausgewählt aus der Gruppe bestehend aus Kronenether, Cryptanden, Tetraalkylammoniumbromiden, insbesondere Tetra-n-butylammoniumbromid, und Triphenylphosphin oder mindestens eine Brönstedt-Base ausgewählt aus der Gruppe bestehend aus Natriumcarbonat, Kaliumcarbonat, Lithiumcarbonat, 1,8-Diazabicyclo[5.4.0]undec-7-en, 1,4-Diazabicyclo[2.2.2]octan, Pyrrolidin, Pyrazol, Imidazol, Harnstoff, Biuret, Dimethylharnstoff, N,N'-Dimethylpropylenharnstoffund Natrium-Dodecylbenzylsulfonsäure als Vernetzer (iii) mindestens einen Vernetzungsbeschleuniger ausgewählt aus der Gruppe bestehend aus Hexamethylendiaminocarbamat, Tetramethylthiuramdisulfid (TMTD), Tetramethylthiurammonosulfid (TMTM), Tetraethylthiuramdisulfid (TETD), Dipentamethylenthiuramdisulfid (DPTD), Zinkisopropylxanthogenat (ZIX), Ethylenthioharstoff (ETU), 1,3-di-o-tolylthioharnstoff (DTTU), Zinkdimethyldithiocarbamat (ZDMC), Zinkdiethyldithiocarbamat (ZDEC), Zinkdibutyldithiocarbamat (ZDBC), Zinkethylphenyldithiocarbamat (ZEPC), Zinkpentamethylendithiocarbamat (ZPD), Natriumdiethyldithiocarbamat (SEDC) und Natriumcyclohexylethyldithiocarbamat (SHEC),
   wobei in der vulkanisierbaren Zusammensetzung andere Vernetzer als die unter (ii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen, bevorzugt nur bis zu 1 Gew. Teil und besonders bevorzugt nur bis zu 0,75 Gew.Teilen, bezogen auf 100 Gew.-Teile des epoxgruppen-haltigen optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind und andere Vernetzungsbeschleuniger als die unter (iii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen, bevorzugt nur bis zu 1 Gew. Teil und besonders bevorzugt nur bis zu 0,75 Gew.Teilen, bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind.

In a particularly preferred embodiment, the vulcanizable composition according to the invention contains

1. (i) at least one epoxy group-containing, optionally wholly or partially hydrogenated nitrile rubber, the repeating units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile, glycidyl acrylate and / or glycidyl methacrylate and optionally one or more other copolymerizable monomers, however contains no non-conjugated cyclic polyene,
2. (ii) at least one Lewis base selected from the group consisting of crown ethers, cryptands, tetraalkylammonium bromides, in particular tetra-n-butylammonium bromide, and triphenylphosphine or at least one Bronsted base selected from the group consisting of sodium carbonate, potassium carbonate, lithium carbonate, 1.8 Diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, pyrrolidine, pyrazole, imidazole, urea, biuret, dimethylurea, N, N'-dimethylpropyleneurea and sodium dodecylbenzylsulfonic acid crosslinker (iii ) at least one crosslinking accelerator selected from the group consisting of hexamethylenediaminocarbamate, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), dipentamethylenethiuram disulfide (DPTD), zinc isopropylxanthogenate (ZIX), ethylene thiocyanate (ETU), 1,3-di-o- tolylthiourea (DTTU), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc phenyl phenyldithiocarbamate (ZEPC), zinc pentamethylene dithiocarbamate (ZPD), sodium diethyldithiocarbamate (SEDC) and sodium cyclohexylethyl dithiocarbamate (SHEC),
   wherein in the vulcanizable composition other crosslinking agents than those mentioned under (ii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 parts by weight, based to 100 parts by weight of the epoxy group-containing optionally completely or partially hydrogenated nitrile rubber (i) are included and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 Gew. Part and more preferably only up to 0.75 parts by weight, based on 100 parts by weight of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) are included.

The conjugated diene in the epoxy group-containing nitrile rubber may be of any nature. Preference is given to using (C ₄ -C ₆ ) conjugated dienes. Particular preference is given to 1,2-butadiene, 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene or mixtures thereof. Particular preference is given to 1,3-butadiene and isoprene or mixtures thereof. Very particular preference is given to 1,3-butadiene.

As α, β-unsaturated nitrile , any known α, β-unsaturated nitrile can be used, preferred are (C ₃ -C ₅ ) -α, β-unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. Particularly preferred is acrylonitrile.

As further copolymerizable monomers it is possible, if desired, for example, to use aromatic vinyl monomers, preferably styrene, α-methylstyrene and vinylpyridine, fluorine-containing vinyl monomers , preferably fluoroethylvinylether, fluoropropylvinylether, o-fluoromethylstyrene, vinylpentafluorobenzoate, difluoroethylene and tetrafluoroethylene, or else copolymerizable antiageing monomers, preferably N- ( 4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamide, N- (4-anilinophenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline and N-phenyl- 4- (4-vinylbenzyloxy) aniline and non-conjugated dienes, such as 4-cyanocyclohexene and 4-vinylcyclohexene, or alkynes, such as 1- or 2-butyne.

Furthermore, hydroxyl-containing monomers may be used as copolymerizable termonomers, preferably hydroxyalkyl (meth) acrylates. However, it is also possible to use appropriately substituted (meth) acrylamines.

Examples of suitable hydroxyalkyl acrylate monomers are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth ) acrylate, glycerol mono (meth) acrylate, hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxymethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylamide, di (ethylene glycol) itaconate, di (propylene glycol) itaconate, bis (2-hydroxypropyl) itaconate, bis (2-hydroxyethyl) itaconate, bis (2-hydroxyethyl ) fumarate, bis (2-hydroxyethyl) maleate and hydroxymethyl vinyl ketone.

Alternatively, carboxy-containing, copolymerizable termonomers can be used as further copolymerizable monomers, for example α, β-unsaturated monocarboxylic acids, their esters, α, β-unsaturated dicarboxylic acids, their mono- or diesters or their corresponding anhydrides or amides.

Acrylic acid and methacrylic acid may preferably be used as α, β-unsaturated monocarboxylic acids .

It is also possible to use esters of α, β-unsaturated monocarboxylic acids, preferably their alkyl esters and alkoxyalkyl esters. Preference is given to the alkyl esters, in particular C ₁ -C ₁₈ alkyl esters of α, β-unsaturated monocarboxylic acids, Particular preference is given to alkyl esters, in particular C ₁ -C ₁₈ alkyl esters of acrylic acid or methacrylic acid, in particular methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert Butyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate. Also preferred are alkoxyalkyl esters of the α, β-unsaturated monocarboxylic acids, particularly preferably alkoxyalkyl esters of acrylic acid or of methacrylic acid, in particular C ₂ -C ₁₂ -alkoxyalkyl esters of acrylic acid or of methacrylic acid, very particularly preferably methoxymethyl acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and methoxyethyl (meth) acrylate. It is also possible to use mixtures of alkyl esters, such as those mentioned above, with alkoxyalkyl esters, for example in the form of the abovementioned. It is also possible to use cyanoalkyl acrylate and cyanoalkyl methacrylate in which the C atom number of the cyanoalkyl group is 2-12, preferably α-cyanoethyl acrylate, β-cyanoethyl acrylate and cyanobutyl methacrylate. It is also possible to use hydroxyalkyl acrylates and hydroxyalkyl methacrylate in which the C atom number of the hydroxyalkyl groups is 1-12, preferably 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 3-hydroxypropyl acrylate; It is also possible to use fluorine-substituted benzyl-containing acrylates or methacrylates, preferably fluorobenzyl acrylate, and fluorobenzyl methacrylate. It is also possible to use fluoroalkyl-containing acrylates and methacrylates, preferably trifluoroethyl acrylate and tetrafluoropropyl methacrylate. It is also possible to use amino-containing αβ-unsaturated carboxylic acid esters, such as dimethylaminomethyl acrylate and diethylaminoethyl acrylate.

Further copolymerizable monomers which can also be used are α, β-unsaturated dicarboxylic acids, preferably maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and mesaconic acid.

It is also possible to use α, β-unsaturated dicarboxylic acid anhydrides, preferably maleic anhydride, itaconic anhydride, citraconic anhydride and mesaconic anhydride.

Can also be used mono- or diesters of α, β-unsaturated dicarboxylic acids.

These α, β-unsaturated dicarboxylic acid mono- or diesters may, for example, be alkyl , preferably C ₁ -C ₁₀ -alkyl, in particular ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl or n-hexyl, alkoxyalkyl, preferably C ₂ -C ₁₂ alkoxyalkyl, particularly preferably C ₃ -C ₈ - alkoxyalkyl, hydroxyalkyl, preferably C ₁ -C ₁₂ hydroxyalkyl, particularly preferably C ₂ -C ₈ -hydroxyalkyl, cycloalkyl, preferably C ₅ -C ₁₂ -cycloalkyl, particularly preferably C ₆ -C ₁₂ -cycloalkyl, alkylcycloalkyl, preferably C ₆ -C ₁₂ -alkylcycloalkyl, particularly preferably C ₇ -C ₁₀ -alkylcycloalkyl, aryl, preferably C ₆ -C ₁₄ -aryl mono- or diesters, which in the case of the diesters may each also be mixed esters.

Particularly preferred alkyl esters of α, β-unsaturated monocarboxylic acids are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, 2-propylheptyl acrylate and lauryl (meth) acrylate. In particular, n-butyl acrylate is used.

Particularly preferred alkoxyalkyl esters of α, β-unsaturated monocarboxylic acids are methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and methoxyethyl (meth) acrylate. In particular, methoxyethyl acrylate is used.

As other esters of α, β-unsaturated monocarboxylic acids, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, N- (2-hydroxyethyl) acrylamides, N- (2-hydroxymethyl) acrylamides and urethane (meth) acrylate are used.

• ● Maleinsäuremonoalkylester, bevorzugt Monomethylmaleat, Monoethylmaleat, Monopropyl maleat und Mono-n-butylmaleat;
• ● Maleinsäuremonocycloalkylester, bevorzugt Monocyclopentylmaleat, Monocyclohexyl maleat und Monocycloheptylmaleat;
• ● Maleinsäuremonoalkylcycloalkylester, bevorzugt Monomethylcyclopentylmaleat und Monoethylcyclohexylmaleat;
• ● Maleinsäuremonoarylester, bevorzugt Monophenylmaleat;
• ● Maleinsäuremonobenzylester, bevorzugt Monobenzylmaleat;
• ● Fumarsäuremonoalkylester, bevorzugt Monomethylfumarat, Monoethylfumarat, Monopropyl fumarat und Mono-n-butyl fumarat;
• ● Fumarsäuremonocycloalkylester, bevorzugt Monocyclopentylfumarat, Monocyclohexyl fumarat und Monocycloheptylfumarat;
• ● Fumarsäuremonoalkylcycloalkylester, bevorzugt Monomethylcyclopentylfumarat und Monoethylcyclohexylfumarat;
• ● Fumarsäuremonoarylester, bevorzugt Monophenylfumarat;
• ● Fumarsäuremonobenzylester, bevorzugt Monobenzylfumarat;
• ● Citraconsäuremonoalkylester, bevorzugt Monomethylcitraconat, Monoethylcitraconat, Monopropylcitraconat und Mono-n-butyl citraconat;
• ● Citraconsäuremonocycloalkylester, bevorzugt Monocyclopentylcitraconat, Monocyclohexyl citraconat und Monocycloheptylcitraconat;
• ● Citraconsäuremonoalkylcycloalkylester, bevorzugt Monomethylcyclopentylcitraconat und Monoethylcyclohexylcitraconat;
• ● Citraconsäuremonoarylester, bevorzugt Monophenylcitraconat;
• ● Citraconsäuremonobenzylester, bevorzgut Monobenzylcitraconat;
• ● Itaconsäuremonoalkylester, bevorzugt Monomethylitaconat, Monoethylitaconat, Monopropyl itaconat und Mono-n-butyl itaconat;
• ● Itaconsäuremonocycloalkylester, bevorzugt Monocyclopentylitaconat, Monocyclohexyl itaconat und Monocycloheptylitaconat;
• ● Itaconsäuremonoalkylcycloalkylester, bevorzugt Monomethylcyclopentylitaconat und Monoethylcyclohexylitaconat;
• ● Itaconsäuremonoarylester, bevorzugt Monophenylitaconat;
• ● Itaconsäuremonobenzylester, bevorzugt Monobenzylitaconat.
• ● Mesaconsäuremonoalkylester, bevorzugt Mesaconsäuremonoethylester;

Examples of α, β-unsaturated dicarboxylic acid monoesters include

• Maleic acid monoalkyl ester, preferably monomethyl maleate, monoethyl maleate, monopropyl maleate and mono-n-butyl maleate;
• Maleic acid monocycloalkyl ester, preferably monocyclopentyl maleate, monocyclohexyl maleate and monocycloheptyl maleate;
• Maleic acid monoalkylcycloalkyl ester, preferably monomethylcyclopentyl maleate and monoethylcyclohexyl maleate;
• Maleic acid monoaryl ester, preferably monophenylmaleate;
• Maleic acid monobenzyl ester, preferably monobenzyl maleate;
• Fumaric acid monoalkyl esters, preferably monomethyl fumarate, monoethyl fumarate, monopropyl fumarate and mono-n-butyl fumarate;
• ● fumaric monocycloalkyl esters, preferably monocyclopentyl fumarate, monocyclohexyl fumarate and monocycloheptyl fumarate;
• Fumaric acid monoalkylcycloalkyl ester, preferably monomethylcyclopentyl fumarate and monoethylcyclohexyl fumarate;
• ● fumaric monoaryl ester, preferably monophenyl fumarate;
• ● Fumaric acid monobenzyl ester, preferably monobenzyl fumarate;
• Citraconic monoalkyl esters, preferably monomethyl citraconate, monoethyl citraconate, monopropyl citrate and mono-n-butyl citraconate;
• Citraconsäuremonocycloalkylester, preferably Monocyclopentylcitraconat, Monocyclohexyl citraconat and Monocycloheptylcitraconat;
• Citraconsäuremonoalkylcycloalkylester, preferably Monomethylcyclopentylcitraconat and Monoethylcyclohexylcitraconat;
• Citraconic monoaryl ester, preferably monophenyl citraconate;
• Citraconic acid monobenzyl ester, preferably monobenzyl citraconate;
• ● itaconic acid monoalkyl ester, preferably monomethyl itaconate, monoethyl itaconate, monopropyl itaconate and mono-n-butyl itaconate;
• ● itaconic acid monocycloalkyl ester, preferably monocyclopentyl itaconate, monocyclohexyl itaconate and monocycloheptyl itaconate;
• ● itaconic acid monoalkylcycloalkyl ester, preferably monomethylcyclopentyl itaconate and monoethylcyclohexyl itaconate;
• ● Itaconic monoaryl ester, preferably monophenyl itaconate;
• ● Itaconic acid monobenzyl ester, preferably monobenzyl itaconate.
• Mesaconsäuremonoalkylester, preferably Mesaconsäuremonoethylester;

As α, β-unsaturated dicarboxylic acid diesters, the analog diesters can be used based on the aforementioned monoester groups, wherein the ester groups may also be chemically different.

Radical polymerizable compounds which contain at least two olefinic double bonds per molecule are also suitable as further copolymerizable monomers. Examples of polyunsaturated compounds are acrylates, methacrylates or itaconates of polyols such as, for example, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, butanediol-1,4-diacrylate, 1,2-propanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, trimethylol propane di (meth) acrylate, trimethylolethane di (meth) acrylate, glycerol di- and triacrylate, pentaerythritol di-, tri- and tetraacrylate or methacrylate, dipentaerythritol tetra, penta and hexaacrylate or methacrylate or itaconate, sorbitol tetraacrylate, sorbitol hexamethacrylate, diacrylates or dimethacrylates of 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 2,2-bis (4-hydroxyphenyl) propane, of polyethylene glycols or of oligoesters or oligourethanes with terminal hydroxyl groups. As polyunsaturated monomers it is also possible to use acrylamides such as, for example, methylene-bisacrylamide, hexamethylene-1,6-bisacrylamide, diethylenetriamine-tris-methacrylamide, bis (methacrylamido-propoxy) ethane or 2-acrylamido-ethyl acrylate. Examples of polyunsaturated vinyl and allyl compounds are divinylbenzene, ethylene glycol divinyl ether, diallyl phthalate, Allyl methacrylate, diallyl maleate, triallyl isocyanurate or triallyl phosphate.

1. (i) mindestens einen Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuk, der Wiederholungseinheiten abgeleitet von a) Acrylnitril, b) 1,3-Butadien, c) mindestens einem Epoxygruppen-haltigen Monomer ausgewählt aus der Gruppe bestehend aus 2-Ethylglycidylacrylat, 2-Ethylglycidylmethacrylat, 2-(n-Propyl) glycidylacrylat, 2-(n-Propyl)glycidylmethacrylat, 2-(n-Butyl)glycidylacrylat, 2-(n-Butyl) glycidylmethacrylat, Glycidylmethylacrylat, Glycidylmethyl-methacrylat, Glycidylacrylat, (3',4'-Epoxyheptyl)-2-ethylacrylat, (3',4'-Epoxyheptyl)-2-ethyl-methacrylat, (6',7'-Epoxy-heptyl)acrylat, (6',7'-Epoxyheptyl)methacrylat, Allylglycidylether, Allyl-3,4-epoxy-heptylether, 6,7-Epoxyheptylallylether, Vinylglycidylether, Vinyl-3,4-epoxyheptylether, 3,4-Epoxyheptylvinylether, 6,7-Epoxyheptylvinylether, o-Vinylbenzylglycidylether, m-Vinylbenzylglycidylether, p-Vinylbenzylglycidylether und 3-Vinylcyclohexenoxid, und d) gegebenenfalls einem oder mehreren weiteren copolymerisierbaren Monomeren, jedoch keinem nicht-konjugierten cyclischen Polyen enthält,
2. (ii) mindestens eine Lewis-Base ausgewählt aus der Gruppe bestehend aus Kronenether, Cryptanden, Tetraalkylammoniumbromiden, insbesondere Tetra-n-butylammoniumbromid, und Triphenylphosphin und/oder eine Brönstedt-Base ausgewählt aus der Gruppe bestehend aus Natriumcarbonat, Kaliumcarbonat, Lithiumcarbonat, 1,8-Diazabicyclo[5.4.0]undec-7-en, 1,4-Diazabicyclo[2.2.2]octan, Pyrrolidin, Pyrazol, Imidazol, Harnstoff, Biuret, Dimethylharnstoff, N,N'-Dimethylpropylenharnstoff oder Natrium-Dodecylbenzylsulfonsäure als Vernetzer und
3. (iii) mindestens einen Vernetzungsbeschleuniger ausgewählt aus der Gruppe bestehend aus Hexamethylendiaminocarbamat, Tetramethylthiuramdisulfid (TMTD), Tetramethylthiurammonosulfid (TMTM), Tetraethylthiuramdisulfid (TETD), Dipentamethylenthiuramdisulfid (DPTD), Zinkisopropylxanthogenat (ZIX), Ethylenthioharstoff (ETU), 1,3-Di-o-tolylthioharnstoff (DTTU), Zinkdimethyldithiocarbamat (ZDMC), Zinkdiethyldithiocarbamat (ZDEC), Zinkdibutyldithiocarbamat (ZDBC), Zinkethylphenyldithiocarbamat (ZEPC), Zinkpentamethylendithiocarbamat (ZPD), Natriumdiethyldithiocarbamat (SEDC) und Natriumcyclohexylethyldithiocarbamat (SHEC),
   wobei in der vulkanisierbaren Zusammensetzung andere Vernetzer als die unter (ii) genannten nur in einer Menge unter 2,5 Gew.-Teilen, bevorzugt nur bis zu 1 Gew. Teil und besonders bevorzugt nur bis zu 0,75 Gew.Teilen, bezogen auf 100 Gew.-Teile des epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind und andere Vernetzungsbeschleuniger als die unter (iii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen, bevorzugt nur bis zu 1 Gew.Teil und besonders bevorzugt nur bis zu 0,75 Gew.Teilen, bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind.

In a preferred embodiment, the vulcanizable composition of the invention contains

1. (i) at least one epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber, the repeat units derived from a) acrylonitrile, b) 1,3-butadiene, c) at least one epoxy group-containing monomer selected from the group consisting of 2-ethylglycidyl acrylate, 2-ethylglycidyl methacrylate, 2- (n-propyl) glycidyl acrylate, 2- (n-propyl) glycidyl methacrylate, 2- (n-butyl) glycidyl acrylate, 2- (n-butyl) glycidyl methacrylate, glycidylmethyl acrylate, glycidylmethyl methacrylate, glycidyl acrylate, (3 ', 4'-epoxyheptyl) -2-ethylacrylate, (3', 4'-epoxyheptyl) -2-ethyl-methacrylate, (6 ', 7'-epoxy-heptyl) acrylate, (6', 7'-epoxyheptyl) methacrylate, allyl glycidyl ether, allyl 3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl glycidyl ether, vinyl 3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether and 3-vinylcyclohexene oxide, and d) optionally one or more further copolymers contains monomers, but does not contain a non-conjugated cyclic polyene,
2. (ii) at least one Lewis base selected from the group consisting of crown ethers, cryptands, tetraalkylammonium bromides, in particular tetra-n-butylammonium bromide, and triphenylphosphine and / or a Bronsted base selected from the group consisting of sodium carbonate, potassium carbonate, lithium carbonate, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, pyrrolidine, pyrazole, imidazole, urea, biuret, dimethylurea, N, N'-dimethylpropyleneurea or sodium dodecylbenzylsulfonic acid as crosslinker and
3. (iii) at least one crosslinking accelerator selected from the group consisting of hexamethylenediaminocarbamate, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), dipentamethylenethiuram disulfide (DPTD), zinc isopropylxanthogenate (ZIX), ethylene thiourea (ETU), 1,3-di o-tolylthiourea (DTTU), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc ethylphenyl dithiocarbamate (ZEPC), zinc pentamethylene dithiocarbamate (ZPD), sodium diethyldithiocarbamate (SEDC), and sodium cyclohexylethyl dithiocarbamate (SHEC).
   wherein in the vulcanizable composition other crosslinking agents than those mentioned under (ii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 parts by weight, based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i) are included and other crosslinking accelerators than the in (iii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 parts by weight, based on 100 parts by weight of Epoxgruppen- containing, optionally completely or partially hydrogenated nitrile rubbers (i) are included.

1. (i) mindestens einen Epoxygruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuk, der Wiederholungseinheiten abgeleitet von a) Acrylnitril, b) 1,3-Butadien, c) Glycidylacrylat und/oder Glycidylmethacrylat und d) gegebenenfalls einem oder mehreren weiteren copolymerisierbaren Monomeren, jedoch keinem nicht-konjugierten cyclischen Polyen enthält,
2. (ii) mindestens eine Lewis-Base ausgewählt aus der Gruppe bestehend aus Kronenether, Cryptanden, Tetraalkylammoniumbromiden, insbesondere Tetra-n-butylammoniumbromid, und Triphenylphosphin und/oder eine Brönstedt-Base ausgewählt aus der Gruppe bestehend aus Natriumcarbonat, Kaliumcarbonat, Lithiumcarbonat, 1,8-Diazabicyclo[5.4.0]undec-7-en, 1,4-Diazabicyclo[2.2.2]octan, Pyrrolidin, Pyrazol, Imidazol, Harnstoff, Biuret, Dimethylharnstoff, N,N'-Dimethylpropylenharnstoff oder Natrium-Dodecylbenzylsulfonsäure als Vernetzer
3. (iii) mindestens einen Vernetzungsbeschleuniger ausgewählt aus der Gruppe bestehend aus Hexamethylendiaminocarbamat, Tetramethylthiuramdisulfid (TMTD), Tetramethylthiurammonosulfid (TMTM), Tetraethylthiuramdisulfid (TETD), Dipentamethylenthiuramdisulfid (DPTD), Zinkisopropylxanthogenat (ZIX), Ethylenthioharstoff (ETU), 1,3-Di-o-tolylthioharnstoff (DTTU), Zinkdimethyldithiocarbamat (ZDMC), Zinkdiethyldithiocarbamat (ZDEC), Zinkdibutyldithiocarbamat (ZDBC), Zinkethylphenyldithiocarbamat (ZEPC), Zinkpentamethylendithiocarbamat (ZPD), Natriumdiethyldithiocarbamat (SEDC) und Natriumcyclohexylethyldithiocarbamat (SHEC)
   wobei in der vulkanisierbaren Zusammensetzung andere Vernetzer als die unter (ii) genannten nur in einer Menge unter 2,5 Gew.-Teilen %, bevorzugt nur bis zu 1 Gew. Teil und besonders bevorzugt nur bis zu 0,75 Gew.Teilen, bezogen auf 100 Gew.-Teile des epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind und andere Vernetzungsbeschleuniger als die unter (iii) genannten nur in einer Menge von unter 2,5 Gew.-Teilen, bevorzugt nur bis zu 1 Gew. Teil und besonders bevorzugt nur bis zu 0,75 Gew.Teilen, bezogen auf 100 Gew.-Teile des Epoxgruppen-haltigen, optional ganz oder teilweise hydrierten Nitrilkautschuks (i) enthalten sind.

In a preferred embodiment, the vulcanizable composition of the invention contains

1. (i) at least one epoxy group-containing, optionally wholly or partially hydrogenated nitrile rubber, the repeat units derived from a) acrylonitrile, b) 1,3-butadiene, c) glycidyl acrylate and / or glycidyl methacrylate and d) optionally one or more further copolymerizable monomers, but does not contain a non-conjugated cyclic polyene,
2. (ii) at least one Lewis base selected from the group consisting of crown ethers, cryptands, tetraalkylammonium bromides, in particular tetra-n-butylammonium bromide, and triphenylphosphine and / or a Bronsted base selected from the group consisting of sodium carbonate, potassium carbonate, lithium carbonate, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, pyrrolidine, pyrazole, imidazole, urea, biuret, dimethylurea, N, N'-dimethylpropyleneurea or sodium dodecylbenzylsulfonic acid as crosslinker
3. (iii) at least one crosslinking accelerator selected from the group consisting of hexamethylenediaminocarbamate, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), dipentamethylenethiuram disulfide (DPTD), zinc isopropylxanthogenate (ZIX), ethylene thiourea (ETU), 1,3-di o-tolylthiourea (DTTU), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc ethylphenyldithiocarbamate (ZEPC), zinc pentamethylene dithiocarbamate (ZPD), sodium diethyldithiocarbamate (SEDC) and sodium cyclohexylethyl dithiocarbamate (SHEC)
   wherein in the vulcanizable composition other crosslinking agents than those mentioned under (ii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 parts by weight, based to 100 parts by weight of the epoxide group-containing, optionally fully or partially hydrogenated nitrile rubber (i) are included and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 parts by weight, based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i) are included.

Proportions of the monomers:

The proportions of the respective monomers in the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubbers to be used according to the invention can vary within wide limits.

The proportion of or the sum of the conjugated dienes is usually in the range from 39.75 to 90% by weight, preferably in the range from 44 to 88% by weight, more preferably from 45.75 to 87 and in particular from 47.5 to 85 Wt .-% based on the total nitrile rubber.

The proportion of or the sum of the α, β-unsaturated nitriles is usually from 5 to 60 wt .-%, preferably from 10 to 55 wt .-%, particularly preferably 13 to 53 wt .-% and in particular 15 to 51 wt. -% based on total nitrile rubber.

The proportion of epoxy group-containing monomers is preferably from 0.25 to 35% by weight, more preferably from 1 to 30% by weight, particularly preferably from 1.25 to 25% by weight and in particular from 1.5 to 18% by weight. % based on total nitrile rubber.

The proportions of all monomers must add up to 100 wt .-% each.

The amount of the epoxy group-containing monomer in the nitrile rubber (i), the amount of the crosslinking agent (ii) and the crosslinking accelerator (iii) and the amount ratio of epoxy groups to crosslinking agent (ii) and crosslinking accelerator (iii) are adjusted depending on the desired degree of crosslinking. By adjusting the ratio of epoxy groups to the amount of crosslinker (ii) and crosslinking accelerator (iii), the elongation at break and tensile stress can be adjusted according to the respective requirements.

Depending on the type, the optional further copolymerizable monomers may be present in amounts of from 0 to 50% by weight, based on the total nitrile rubber (i). In this case, corresponding proportions of the conjugated diene (s) and / or the α, β-unsaturated nitriles and / or the epoxy group-containing monomer are replaced by the proportions of the additional monomers, the proportions of all the monomers again being in each case 100% by weight .-% have to sum up.

The preparation of such epoxy group-containing, optionally completely or partially hydrogenated nitrile rubbers is well known to the person skilled in the art. The epoxy group-containing nitrile rubber is usually prepared by a so-called emulsion polymerization. This is carried out in the presence of emulsifiers which are typically water-soluble salts of anionic emulsifiers or neutral emulsifiers. Furthermore, polymerisation is frequently carried out in the presence of so-called molecular weight regulators, which are generally alkylthiols containing 12-16 carbon atoms, preferably tert-dodecylmercaptans (t-DDM). Such alkylthiols or (isomeric) mixtures of alkylthiols are either commercially available or can be prepared by those skilled in the art by methods which are well described in the literature.

To carry out the polymerization, all or individual components of the initiator system are added at the beginning of the polymerization and / or during the polymerization. The addition in portions of all and individual components during the polymerization is preferred. By a sequential addition, the reaction rate can be controlled. To achieve a uniform course of polymerization, only part of the initiator system is used for the start of the polymerization, and the remainder is metered in during the polymerization. Usually, the polymerization is started with 10 to 80% by weight, preferably 30-50% by weight, of the total amount of initiator. The addition of individual components of the initiator system is possible. If you want to produce chemically uniform products, the monomers are dosed. In particular, acrylonitrile and butadiene are replenished when the composition is outside the azeotropic butadiene / acrylonitrile ratio. Preference is given to replenishing with NBR types having acrylonitrile contents of from 10 to 34% by weight and also of the types containing from 40 to 50% by weight of acrylonitrile ( W. Hofmann, Rubber Chem. Technol. 36 (1963 ). The polymerization time is in the range of 5 h to 15 h and depends above all on the acrylonitrile content of the monomer mixture and on the polymerization temperature. The latter is in the range of 0 to 30 ° C, preferably in the range of 5 to 25 ° C. Upon achieving conversions in the range of 50 to 90%, preferably in the range of 60 to 85%, the polymerization is typically terminated by the addition of a common stopper. The amount of water used in the emulsion polymerization is in the range of 100 to 900 parts by weight, preferably in the range of 120 to 500 parts by weight, more preferably in the range of 150 to 400 parts by weight of water based on 100 parts by weight the monomer mixture. The polymerization can be carried out either batchwise or continuously in a stirred tank cascade. To remove unreacted monomers and volatile components of the stopped latex is subjected to a steam distillation. In this case, temperatures in the range of 70 ° C to 150 ° C are used, wherein at temperatures <100 ° C, the pressure is reduced. Before the removal of the volatile constituents, a post-stabilization of the latex with emulsifier can take place. For this purpose, it is expedient to use the abovementioned emulsifiers in amounts of 0.1 to 2.5% by weight, preferably 0.5 to 2.0% by weight. % based on 100 parts by weight of nitrile rubber.

Metathesis and hydrogenation:

It is also possible that the preparation of the epoxy group-containing nitrile rubber (a) is followed by a metathesis reaction for reducing the molecular weight of the nitrile rubber or (b) a metathesis reaction and a subsequent hydrogenation or (c) only one hydrogenation. These metathesis or hydrogenation reactions are well known in the art and described in the literature. For example, the metathesis is off , WO-A-02/100941 as well as the WO-A-02/100905 known and can be used for molecular weight reduction.

The hydrogenation can be carried out using homogeneous or heterogeneous hydrogenation catalysts. The catalysts used are usually based on rhodium, ruthenium or titanium, but it is also possible to use platinum, iridium, palladium, rhenium, ruthenium, osmium, cobalt or copper either as metal or preferably in the form of metal compounds (see, for example, US Pat US-A-3,700,637 . DE-A-25 39 132 . EP-A-0 134 023 . DE-OS 35 41 689 . DE-OS 35 40 918 . EP-A-0 298 386 . DE-OS 35 29 252 . DE-OS 34 33 392 . US-A-4,464,515 and US-A-4,503,196 ).

Suitable catalysts and solvents for homogeneous phase hydrogenation are described below and are also exhaustive DE-A-25 39 132 and the EP-A-0 471 250 known. The selective hydrogenation can be achieved, for example, in the presence of a rhodium- or ruthenium-containing catalyst. It is possible, for example, to use a catalyst of the general formula

(R ¹ _m B) ₁ MX _n ,

wherein M is ruthenium or rhodium, R ^{1 are the} same or different and represent a C ₁ -C ₈ alkyl group, a C ₄ -C ₈ cycloalkyl group, a C ₆ -C ₁₅ aryl group or a C ₇ -C ₁₅ aralkyl group. B is phosphorus, arsenic, sulfur or a sulfoxide group S = O, X is hydrogen or an anion, preferably halogen and more preferably chlorine or bromine, 1 is 2,3 or 4, m is 2 or 3 and n is 1, 2 or 3, preferably 1 or 3. Preferred catalysts are tris (triphenylphosphine) rhodium (I) chloride, tris (triphenylphosphine) rhodium (III) chloride and tris (dimethyl sulfoxide) rhodium (III) chloride and tetrakis ( triphenylphosphine) rhodium hydride of the formula (C ₆ H ₅ ) ₃ P) ₄ RhH and the corresponding compounds in which the triphenylphosphine has been wholly or partly replaced by tricyclohexylphosphine. The catalyst can be used in small quantities. An amount in the range of 0.01-1% by weight, preferably in the range of 0.03-0.5% by weight, and more preferably in the range of 0.1-0.3% by weight based on the weight of the polymer are suitable.

It is usually useful to use the catalyst together with a co-catalyst which is a ligand of the formula R ¹ _m B, where R ¹ , m and B have the meanings given above for the catalyst. Preferably m is 3, B is phosphorus and the radicals R ¹ may be the same or be different. Preference is given to co-catalysts with trialkyl, tricycloalkyl, triaryl, triaralkyl, diaryl-monoalkyl, diaryl-monocycloalkyl, dialkyl-monoaryl, dialkylmonocycloalkyl, dicycloalkyl-monoaryl or dicyclalkyl-monoaryl radicals.

Examples of co-catalysts can be found, for example, in US-A-4,631,315 , Preferred co-catalyst is triphenylphosphine. The co-catalyst is preferably used in amounts in a range of 0.3-5 wt.%, Preferably in the range of 0.5-4 wt.%, Based on the weight of the nitrile rubber to be hydrogenated. Furthermore, the weight ratio of the rhodium-containing catalyst to the cocatalyst is preferably in the range from 1: 3 to 1:55, particularly preferably in the range from 1: 5 to 1:45, based on 100 parts by weight of the nitrile rubber to be hydrogenated, preferably 0, 1 to 33 parts by weight of the co-catalyst, preferably 0.5 to 20 and very particularly preferably 1 to 5 parts by weight, in particular more than 2 but less than 5 parts by weight of co-catalyst based on 100 parts by weight of the nitrile rubber to be hydrogenated.

The practical implementation of the hydrogenation is the expert from US-A-6,683,136 known. It is usually carried out by subjecting the nitrile rubber to be hydrogenated in a solvent such as toluene or monochlorobenzene at a temperature in the range of 100 to 150 ° C and a pressure in the range of 50 to 150 bar for 2 to 10 hours with hydrogen.

In the context of this invention, hydrogenation is understood as meaning a conversion of the double bonds present in the starting nitrile rubber to at least 50%, preferably 70-100%, particularly preferably 80-100%. The determination of the degree of hydrogenation is well known to the person skilled in the art and can be carried out, for example, by Raman or IR spectroscopy (see, for example, US Pat EP-A-0 897 933 for determination by Raman spectroscopy or US-A-6,522,408 for determination by IR spectroscopy).

When using heterogeneous catalysts are usually supported catalysts based on palladium, z. B. supported on carbon, silica, calcium carbonate or barium sulfate.

In this case, epoxy-group-containing completely or partially hydrogenated nitrile rubbers are obtained. These have repeating units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile and optionally one or more other copolymerizable monomers, but no non-conjugated cyclic polyene.

These epoxy group-containing, optionally wholly or partially hydrogenated nitrile rubbers usually have Mooney viscosities (ML (1 + 4 @ 100 ° C)) in the range of 10 to 160, preferably from 15 to 150 Mooney units, more preferably from 20 to 150 Mooney units and in particular 25 to 145 Mooney units. The values for the Mooney viscosity (ML 1 + 4 @ 100 ° C.) are determined by means of a shear disk viscometer in accordance with DIN 53523/3 or ASTM D 1646 at 100 ° C.

The epoxy group-containing, optionally wholly or partially hydrogenated nitrile rubbers typically also have a polydispersity PDI = M _w / M _n , where M _{w is} the weight average and M _{n is} the number average molecular weight, in the range of 1.0 to 6.0 and preferred in the range of 1.5 to 5.0.

The glass transition temperatures of the epoxy group-containing, optionally wholly or partially hydrogenated nitrile rubbers are in the range of -80 ° C to + 20 ° C, preferably in the range of -70 ° C to + 10 ° and more preferably in the range of -60 ° C to 0 ° C.

In a preferred embodiment of the invention are vulcanizable compositions which (iv) additionally contain at least one filler. These fillers are exclusively compounds which are not already covered by the crosslinkers (ii) or crosslinking accelerators (iii) according to the invention. It is possible to use, for example, Carbon black, silica, carbon nanotubes, teflon (the latter preferably in powder form) or silicates.

In further embodiments, the vulcanizable compositions according to the invention may also contain one or more additives familiar to the rubber expert. These too are exclusively compounds which do not fall under the definition of the crosslinkers (ii) or crosslinking accelerators (iii) according to the invention. These additives include filler activators, anti-aging agents, anti-reversion agents, light stabilizers, antiozonants, processing aids, plasticizers, mineral oils, tackifiers, blowing agents, dyes, pigments, waxes, resins, extenders, cure retarders, as well as other or other additives known in the rubber industry (US Pat. Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, vol. A 23 "Chemicals and Additives", pp. 366-417 ).

Suitable filler activators are, for example, organic silanes, preferably vinyltrimethyloxysilane, vinyldimethoxymethylsilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N-cyclohexyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, Isooctyltrimethoxysilane, isooctyltriethoxysilane, hexadecyltrimethoxysilane or (octadecyl) methyldimethoxysilane. Further filler activators are, for example, surface-active substances such as triethanolamine, trimethylolpropane, hexanetriol and polyethylene glycols having molecular weights of 74 to 10,000 g / mol. The amount of filler activators is usually 0 to 10 parts by weight, based on 100 parts by weight of the epoxide group-containing , optionally completely or partially hydrogenated nitrile rubber.

As anti- aging agents, it is possible to add to the vulcanizable compositions all those known to the person skilled in the art, which are customary in amounts of 0 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the epoxide group-containing hydrogenated nitrile rubbers are used.

Suitable mold release agents are, for example, saturated or partially unsaturated fatty and oleic acids and derivatives thereof (fatty acid esters, fatty acid salts, fatty alcohols, fatty acid amides). Furthermore, it is possible to use products which can be applied to the mold surface, such as, for example, products based on low molecular weight silicone compounds, products based on fluoropolymers and products based on phenolic resins. The mold release agents are used in amounts of 0 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the epoxide group-containing, optionally hydrogenated nitrile rubber.

Also the reinforcement with strength members (fibers) made of glass, according to the doctrine of US Patent No. 4,826,721 is possible as well as the reinforcement by cords, fabrics, fibers of aliphatic and aromatic polyamides (Nylon®, Aramid®), polyesters and natural fiber products.

The invention further provides the process for the preparation of the vulcanizable compositions by mixing at least one epoxy group-containing, completely or partially hydrogenated nitrile rubber (i) with at least one Lewis and / or Bronsted acid (ii) and at least one crosslinking accelerator (iii). This mixing process can be carried out in all mixing apparatuses familiar to the person skilled in the art. Usually, the at least one crosslinker (ii) and the at least one crosslinking accelerator (iii) are added to the nitrile rubber (i). If one or more fillers and one or more other rubber additives are used, these can also be mixed in any order.

The invention further provides a process for the preparation of vulcanizates based on an epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber, characterized in that the aforementioned vulcanizable composition is crosslinked with increasing temperature. The crosslinking may take place at temperatures in the range of preferably 20 to 250 ° C, more preferably 50 to 230 ° C take place. The duration of the crosslinking reaction is in the range of one (1) minute to several days.

The invention also relates to the vulcanizates obtainable in this way. These vulcanizates contain crosslinked epoxy group-containing, optionally completely or partially hydrogenated nitrile rubbers. They show very good values in the compression set test at room temperature, 100 ° C. and 150 ° C. and furthermore a high tensile stress with good elongation at break.

Claims (13)

Containing vulcanizable composition (I) at least one epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber containing repeating units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile and optionally one or more other copolymerizable monomers, but no non-conjugated cyclic polyene (ii) at least one Lewis and / or Bronsted base as crosslinker, (iii) at least one crosslinking accelerator selected from the group consisting of thiurams, xanthogenates, thioureas, dithiocarbamates and carbamates,
wherein the Lewis and / or Bronsted base (ii) must be different from the defined group of crosslinking accelerators (iii), and in the vulcanizable composition other crosslinkers than those mentioned under (ii) only in an amount of less than 2.5 wt Parts based on 100 parts by weight of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) are included and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight to 100 parts by weight of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) are included .. Vulcanisable composition according to claim 1, characterized in that they are each based on 100 parts by weight of the eopxy-containing, optionally completely or partially hydrogenated nitrile rubber (i) not more than 2.3 parts by weight of crosslinking agents other than those mentioned under (ii) and, at the same time, other crosslinking accelerators than those mentioned under (iii), up to a maximum of 2.3 parts by weight, preference is given to crosslinking agents other than those specified under (ii), up to a maximum of 2.25 parts by weight, and at the same time other crosslinking accelerators than those mentioned under (iii), up to a maximum of 2.25 parts by weight, particularly preferably crosslinking agents other than those mentioned under (ii), up to a maximum of 2 parts by weight and simultaneously other crosslinking accelerators than those mentioned under (iii), up to a maximum of 2 parts by weight, very particular preference is given to cross-linking agents other than those mentioned under (ii) up to a maximum of 1.5 parts by weight, and at the same time other crosslinking accelerators than those mentioned under (iii), up to a maximum of 1.5% by weight. Share, in particular crosslinking agents other than those mentioned under (ii), up to a maximum of 1 part by weight and at the same time other crosslinking accelerators than those mentioned under (iii), up to a maximum of 1 part by weight, Particular preference is given to cross-linking agents other than those specified under (ii) up to a maximum of 0.5 parts by weight and cross-linking accelerators other than those mentioned under (iii), up to a maximum of 0.5 parts by weight, - Particularly particularly preferred crosslinking agents other than those mentioned under (ii) up to a maximum of 0.4 parts by weight,. and crosslinking accelerators other than those mentioned under (iii) at most up to an amount of 0.4 parts by weight and - most preferably no crosslinking agent other than those mentioned under (ii) and no crosslinking accelerators at all other than those mentioned under (iii). Vulcanisable composition according to claim 1 or 2, characterized in that as Lewis base (s) crown ethers, in particular 12-crown-4, cryptands, in particular [2.2.2] cryptand, ammonia, tetraalkylammonium salts, especially tetraalkylammonium bromides, Benzyltrialkylammoniumsalze, tetraalkylphosphonium salts, Benzyltrialkylphosphoniumsalze, triphenylphosphine, sodium or potassium cyanide, sodium iodide, bipyridine, phenantroline, tetrahydrofuran, cyclooctadiene, hydrazine or diethyl ether are used. Vulcanisable composition according to one of claims 1 to 3, characterized in that as Bronsted base (s) those selected from the group consisting of sulfates, sulfites, sulfides, phosphates, carbonates, substituted or unsubstituted amines, substituted or unsubstituted, aromatic or not aromatic nitrogen-containing organic heterocycles, substituted or unsubstituted urea derivatives, guanidines and derivatives thereof, hydroxides of alkali or alkaline earth metals, salts of inorganic or organic sulfonic, carboxylic and phophonic acids, their mono- or diesters and organometallic compounds of the alkali metals lithium, sodium and potassium are used. A vulcanizable composition according to claim 1 comprising (I) at least one epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber containing repeating units derived from at least one conjugated diene, at least one α, β-unsaturated nitrile and optionally one or more other copolymerizable monomers, but no non-conjugated cyclic polyene . (ii) at least one Lewis base selected from the group consisting of crown ethers, cryptands, tetraalkylammonium bromides, in particular tetra-n-butylammonium bromide, triphenylphosphine and bipyridine and / or a Bronsted base selected from the group consisting of sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate , Triethylamine, diisopropylamine, triethanolamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, tetramethylethylenediamine, pyrrolidine, pyrazole, piperidine, pyrrole, imidazole, urea , Biuret, dimethylurea, N, N'-dimethylpropyleneurea and sodium dodecylbenzylsulfonic acid as crosslinker, (iii) at least one crosslinking accelerator selected from the group consisting of hexamethylenediaminocarbamate, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), dipentamethylene thiuram monosulfide (DPTM), dipentamethylene thiuram disulfide (DPTD), dimethyl diphenyl thiuram disulfide (MPTD ), Arylguanidinium xanthogenates, zinc isopropylxanthogenate (ZIX), ethylene thiourea (ETU), diphenylthiourea (DPTU), 1,3-di-o-tolylthiourea (DTTU), diethyltiourea (DPTU), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC ), Zinc ethylenedithiocarbamate (ZEPC), zinc dibenzyldithiocarbamate (ZDBC), zinc pentamethylene dithiocarbamate (ZPD), sodium diethyldithiocarbamate (SEDC), sodium dimethyldithiocarbamate (SMDC), sodium dibutyldithiocarbamate (SBC), and sodium cyclohexylethyldithiocarbamate (SHEC).
wherein in the vulcanizable composition other crosslinking agents than those mentioned under (ii) only in an amount of less than 2.5 parts by weight, preferably up to 1 part by weight and particularly preferably up to 0.75 part by weight, based on 100 parts by weight of the epoxy group-containing optionally completely or partially hydrogenated nitrile rubber (i) are contained and and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight, preferably up to 1 wt . Part, and more preferably up to 0.75 Gew.Teil, based on 100 parts by weight of the epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber (i) are included. Vulcanisable composition according to one of claims 1 to 5, characterized in that as epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i) is used one in which the epoxy groups by subsequent grafting or grafting of epoxy group-containing compounds on the nitrile rubber or one such, the repeating units of at least one nitrile, at least one conjugated diene, at least one epoxy group-containing monomer and optionally one or more other copolymerizable monomers, but not unconjugated cyclic polyenes. Vulcanisable composition according to one of claims 1 to 6, characterized in that the epoxide group-containing, fully or partially hydrogenated nitrile rubber (i) repeating units of an epoxy group-containing monomers of the general formula (I)

wherein, m is 0 or 1 and X is O, O (CR ₂ ) _p , (CR ₂ ) _p O, C (= O) O, C (= O) O (CR ₂ ) _p , C (= O) NR, (CR ₂ ) _p , N (R), N (R) (CR ₂ ) _p , P (R), P (R) (CR ₂ ) _p , P (= O) (R), P (= O) (R) (CR ₂ ) _p , S, S (CR ₂ ) _p , S (= O), S (= O) (CR ₂ ) _p , S (= O) ₂ (CR ₂ ) _p or S (= O) ₂ where R in these radicals may have the same meanings as R ¹ -R ⁶ Y represents repeating units of one or more mono- or polyunsaturated monomers, comprising conjugated or non-conjugated dienes, alkynes and vinyl compounds, or a structural element derived from polymers comprising polyethers, in particular polyalkylene glycol ethers and polyalkylene oxides, polysiloxanes, polyols, polycarbonates , Polyurethanes, polyisocyanates, polysaccharides, polyesters and polyamides, n and p are the same or different and are each in the range of 0 to 10,000, R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are the} same or different and are H, a linear or branched, saturated, mono- or polyunsaturated alkyl radical, a saturated, mono- or polyunsaturated Carbo or heterocyclyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, alkoxy, aryloxy, heteroaryloxy, amino, amido, carbamoyl, alkylthio, arylthio, sulfanyl, thiocarboxy, sulfinyl, sulfono, sulfino, sulfeno, sulfonic acids, sulfamoyl, hydroxyimino, alkoxycarbonyl, F, Cl, Br, I, hydroxy, phosphonato, phosphinato, silyl, silyloxy, nitrile, borates, selenates, carbonyl, carboxy, oxycarbonyl, oxysulfonyl, oxo, thioxo, epoxy, cyanates, thiocyanates, isocyanates, thioisocyanates or isocyanides, Vulcanisable composition according to one of claims 1 to 7, characterized in that the epoxide group-containing fully or partially hydrogenated nitrile rubber (i) repeating units of an epoxy group-containing monomer contains selected from the group 2-ethylglycidyl acrylate, 2-ethylglycidyl methacrylate, 2- (n-propyl) glycidyl acrylate, 2- (n-propyl) glycidyl methacrylate, 2- (n-butyl) glycidyl acrylate, 2- (n-butyl) glycidyl methacrylate, glycidyl methacrylate , Glycidylmethyl methacrylate, glycidyl acrylate, (3 ', 4'-epoxyheptyl) -2-ethylacrylate, (3', 4'-epoxyheptyl) -2-ethylmethacrylate, (6 ', 7'-epoxyheptyl) acrylate, (6', 7 ' Epoxyheptyl) methacrylate, allyl glycidyl ether, allyl 3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl glycidyl ether, vinyl 3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether , p-vinylbenzylglycidyl ether and 3-vinylcyclohexene oxide. A vulcanizable composition according to claim 1 or 2, comprising (i) at least one epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber, the repeat units derived from a) acrylonitrile, b) 1,3-butadiene, c) at least one epoxy group-containing monomer selected from the group consisting of 2-ethylglycidyl acrylate, 2-ethylglycidyl methacrylate, 2- (n-propyl) glycidyl acrylate, 2- (n-propyl) glycidyl methacrylate, 2- (n-butyl) glycidyl acrylate, 2- (n-butyl) glycidyl methacrylate, glycidyl methacrylate, glycidylmethyl methacrylate, glycidyl acrylate, (3 ', 4'-epoxyheptyl) -2-ethyl acrylate, (3', 4'-epoxyheptyl) -2-ethyl-methacrylate, (6 ', 7'-epoxyheptyl) acrylate, (6', 7'-epoxyheptyl) methacrylate, Allyl glycidyl ether, allyl 3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl glycidyl ether, vinyl 3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p- Vinylbenzylglycidylether and 3-vinylcyclohexene oxide, and d) optionally copolymerizable one or more further contains monomers but no non-conjugated cyclic polyene, (ii) at least one Lewis base selected from the group consisting of crown ethers, cryptands, tetraalkylammonium bromides, in particular tetra-n-butylammonium bromide, and triphenylphosphine and / or a Bronsted base selected from the group consisting of sodium carbonate, potassium carbonate, lithium carbonate, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, pyrrolidine, pyrazole, imidazole, urea, biuret, dimethylurea, N, N'-dimethylpropyleneurea or sodium dodecylbenzylsulfonic acid Crosslinkers and (iii) at least one crosslinking accelerator selected from the group consisting of hexamethylenediaminocarbamate, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), Dipentamethylenethiuram disulfide (DPTD), zinc isopropylxanthogenate (ZIX), ethylene thiourea (ETU), 1,3-di-o-tolylthiourea (DTTU), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc ethylphenyl dithiocarbamate (ZEPC), zinc pentamethylene dithiocarbamate (DPTD). ZPD), sodium diethyldithiocarbamate (SEDC) and sodium cyclohexylethyldithiocarbamate (SHEC),
wherein in the vulcanizable composition other crosslinking agents than those mentioned under (ii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 parts by weight, based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i) are contained and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 Gew.Teil and particularly preferably only up to 0.75 Gew.Teilen, based on 100 parts by weight of the Epoxgruppen-containing, optionally completely or partially hydrogenated nitrile rubber (i) are contained. A vulcanizable composition according to claim 1 or 2, comprising (i) at least one epoxy group-containing, optionally wholly or partially hydrogenated nitrile rubber, the repeat units derived from a) acrylonitrile, b) 1,3-butadiene, c) glycidyl acrylate and / or glycidyl methacrylate and d) optionally one or more further copolymerizable monomers, but does not contain a non-conjugated cyclic polyene, (ii) at least one Lewis base selected from the group consisting of crown ethers, cryptands, Tetraalkylammoniumbromiden, especially tetra-n-butylammonium bromide, and triphenylphosphine and / or a Bronsted base selected from the group consisting of sodium carbonate, potassium carbonate, lithium carbonate, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, pyrrolidine, pyrazole, imidazole, urea, biuret, dimethylurea, N, N'-dimethylpropyleneurea or sodium dodecylbenzylsulfonic acid crosslinkers (iii) at least one crosslinking accelerator selected from the group consisting of hexamethylenediaminocarbamate, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), dipentamethylenethiuram disulfide (DPTD), zinc isopropylxanthogenate (ZIX), ethylene thiourea (ETU), 1,3-di o-tolylthiourea (DTTU), zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc ethylphenyl dithiocarbamate (ZEPC), zinc pentamethylene dithiocarbamate (ZPD), sodium diethyldithiocarbamate (SEDC), and sodium cyclohexylethyl dithiocarbamate (SHEC).
wherein in the vulcanizable composition other crosslinking agents than those mentioned under (ii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 parts by weight, based to 100 parts by weight of the epoxide group-containing, optionally fully or partially hydrogenated nitrile rubber (i) are included and other crosslinking accelerators than those mentioned under (iii) only in an amount of less than 2.5 parts by weight, preferably only up to 1 part by weight and more preferably only up to 0.75 parts by weight, based on 100 parts by weight of the epoxy group-containing, optionally completely or partially hydrogenated nitrile rubber (i) are included. A process for preparing a vulcanizable composition according to any one of claims 1 to 10 by mixing at least one epoxy group-containing, fully or partially hydrogenated nitrile rubber (i) with at least one Lewis and / or Bronsted base (ii) and at least one crosslinking accelerator (iii). , A process for the preparation of vulcanizates based on an epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber, characterized in that the vulcanizable composition according to any one of claims 1 to 10 with increasing the temperature, preferably in the range of 20 to 250 ° C, particularly preferred is crosslinked in the range of 50 to 230 ° C. Vulcanizates based on a crosslinked epoxy group-containing, optionally fully or partially hydrogenated nitrile rubber according to one of claims 1 to 10.